Personal care compositions

ABSTRACT

Relatively low VOC hair styling compositions which provide good style retention without unacceptable stickiness or stiffness are disclosed. The compositions comprise from about 0.01% to about 20%, by weight of the composition, of a hair styling polymer; and a carrier comprising at least about 0.5% to about 99.9%, by weight of the composition, of a first solvent selected from the group consisting of water; water soluble organic solvents; organic solvents which are strongly to moderately strong in hydrogen bonding parameter; and mixtures thereof; wherein the first solvent is other than C1-C3 monohydric alcohol, C1-C3 ketone, and C1-C3 ether; and from about 0% to about 55%, by weight of the composition, of a second solvent selected from the group consisting of C1-C3 monohydric alcohols, C1-C3 ketones, C1-C3 ethers, and mixtures thereof; wherein the composition is characterized by having a Stiffness Value (SV) and a Curl Retention Index (CRI), wherein SV≧[(0.703×CRI)-0.425)].

TECHNICAL FIELD

The present invention relates to relatively low VOC hair stylingcompositions, e.g., mousses and gels, containing a hair styling polymerand a carrier comprising, e.g., water and optionally lower monohydricalcohol. The compositions are characterized by providing both good stylehold and hair feel. The composition, when dried, exhibits a StiffnessValue (SV) and a Curl Retention Index (CRI) wherein the SV is at least[(0.703×CRI)-0.425].

BACKGROUND OF THE INVENTION

The desire to have the hair retain a particular style or shape is widelyheld. The most common methodology for accomplishing this is by sprayinga composition, typically from a mechanical pump spray device or from apressurized aerosol canister, to the hair. Other means of providingstyle or shaping to the hair are mousses, gels, lotions and the like.Such compositions provide temporary setting benefits and can usually beremoved by water or by shampooing. The materials used in these types ofhair styling compositions are generally resins, gums, and adhesivepolymers which are capable of imparting style or shape to the hair. Manyof these products also contain lower alcohols in order to obtain goodfilms of the polymer in a short period of time.

Many people desire a high level of style retention, or hold, from astyling product. Unfortunately, most current hair styling productshaving good hold characteristics suffer from the disadvantages of beingeither too stiff, not smooth or too sticky upon drying Stiffcompositions tend to be brittle and break down under common stressessuch as wind, brushing, combing. Stiff compositions also tend to feeland look unnatural. Sticky compositions overcome many of the foregoingdisadvantages of stiff compositions, because sticky compositions tend tobe more forgiving, i.e., flexible, under stress and allow for restylingof the hair. However, sticky compositions have the disadvantage ofleaving the hair with a heavy, coated feel and with a limp andunattractive appearance. Also, sticky compositions cause the hair toquickly become soiled from common contaminant sources such as dust,dirt, lint, sebum, etc.

One approach to minimizing stiffness and roughness of a hair stylingcomposition is the incorporation of silicones, including siliconeemulsions and microemulsions, in such compositions. Silicones tend toprovide a desirably smooth or soft hair feel. Unfortunately, siliconeemulsions tend to be difficult to formulate in hair stylingcompositions. Hair styling compositions tend to be complex, requiring anumber of ingredients for different purposes, with potential forincompatibilities. For example, silicone emulsions tend to be unstablein compositions containing lower alcohols, resulting in phase separationof the composition. Other incompatibilities in the system, e.g.,polymer-polymer or polymer-surfactant interactions, can also result inphase separation. This phase separation is not only undesirable forvisual esthetic reasons, but for performance reasons as well. When theproduct phase separates, hold and/or hair feel properties of the producttend to be negatively impacted.

Therefore, a need exists for hair styling compositions providing goodstyle retention without the disadvantages of stiff or stickycompositions. There is a particular need for hair styling compositionscontaining lower alcohols providing good style retention without thedisadvantages of stiff or sticky compositions.

Surprisingly, the present invention provides hair styling compositionshaving good style retention without being stiff or sticky. The resultinghair styles obtained from using these compositions hold up well underthe common stress conditions and other factors as mentioned above.Importantly, such compositions provide the benefit of allowing the userto restyle the hair without the need for reapplication of stylingproduct. The styling compositions of the present invention leave thehair both feeling and looking natural. Also, these products do not havethe disadvantage of causing the hair to quickly resoil.

It has been found in the present invention that compositions havingcertain properties, as defined by a Stiffness Value (SV) and a CurlRetention Index (CRI), are particularly useful for providing strong holdin combination with good hair feel. The hair styling compositions, whendried, exhibit a Stiffness Value (SV) and a Curl Retention Index (CRI)wherein the SV is at least equal to [(0.703×CRI)-0.425)]. Thecompositions of the present invention provide the recited benefits byutilizing a hair styling polymer. Compositions of this type are providedeven where the composition contains relatively high levels of loweralcohols.

It is therefore an object of this invention to provide hair stylingcompositions that provide good style retention without unacceptablestiffness or stickiness. Another object of this invention is to providehair styling compositions that both look and feel natural.

It is another object of this invention to provide hair stylingcompositions containing silicone microemulsions, especially compositionswhich also contain lower alcohol.

It is another object of this invention to provide methods for stylingand holding hair.

These and other objects will become readily apparent from the detaileddescription which follows.

SUMMARY OF THE INVENTION

The present invention relates to personal care compositions, especiallysuch compositions which are suitable for styling hair. The compositionscomprise:

a) from about 0.01% to about 20%, by weight of the composition, of ahair styling polymer; and

b) a carrier comprising:

i) at least about 0.5% to about 99.9%, by weight of the composition, ofa first solvent selected from the group consisting of water; watersoluble organic solvents; organic solvents which are strongly tomoderately strong in hydrogen bonding parameter; and mixtures thereof;wherein the first solvent is other than C1-C3 monohydric alcohol, C1-C3ketone, and C1-C3 ether; and

ii) from about 0% to about 55%, by weight of the composition, of asecond solvent selected from the group consisting of C1-C3 monohydricalcohols, C1-C3 ketones, C1-C3 ethers, and mixtures thereof;

wherein the composition is characterized by providing a Stiffness Value(SV) and a Curl Retention Index (CRI), wherein SV≧[(0.703×CRI)-0.425)].

In a preferred embodiment, SV≧[(0.703×CRI)-0.80]. In a more preferredembodiment, SV≧[(0.703×CRI)-1.55].

DETAILED DESCRIPTION OF THE INVENTION

The essential components of the present invention are described below.Also included is a nonexclusive description of various optional andpreferred components useful in embodiments of the present invention.

The present invention can comprise, consist of, or consist essentiallyof any of the required or optional ingredients and/or limitationsdescribed herein.

All percentages and ratios are calculated on a weight basis unlessotherwise indicated. All percentages are calculated based upon the totalcomposition unless otherwise indicated.

All molecular weights are weight average molecular weights and are givenin units of grams per mole.

All ingredient levels are in reference to the active level of thatingredient, and are exclusive of solvents, by-products, or otherimpurities that may be present in commercially available sources, unlessotherwise indicated.

All measurements made are at ambient room temperature, which isapproximately 73° F., unless otherwise designated.

All documents referred to herein, including all patents, patentapplications, and printed publications, are hereby incorporated byreference in their entirety in this disclosure.

The term "suitable for application to human hair" as used herein, meansthat the compositions or components thereof so described are suitablefor use in contact with human hair and the scalp and skin without unduetoxicity, incompatibility, instability, allergic response, and the like.

Hair Styling Polymers

The compositions of the present invention comprise a hair stylingpolymer for providing stylability to the hair. Hair styling polymerspossess adhesive properties such that they are capable of shaping orstyling the hair, and should be removable by shampooing or rinsing thehair. One or more hair styling polymers may be used. The total amount ofhair styling polymer is generally from about 0.01% to about 20%,preferably from about 0.1% to about 15%, more preferably from about 0.5%to about 10%. A variety of hair styling polymers are suitable in thepresent invention. Particular polymers will be selected by the skilledartisan considering the solubility of the polymer in the composition andthe ionicity of the composition.

Suitable hair styling polymers are those which are soluble ordispersible (preferably microdispersible) in the carrier describedherein in the weight ratios employed in the composition. Solubility isdetermined at ambient conditions of temperature and pressure (25° C.,101.3 kPa (1 Atm)). Solubility/dispersibility of the polymer should bedetermined after neutralization, if any.

In addition, the hair polymers and the other components (e.g.,surfactants) are selected such that the total composition will becompatible such that a substantially homogeneous solution or dispersion(preferably a microdispersion) is formed.

Incompatibility is typically evidenced by marked phase separation, e.g.,excessive cloudiness, layering or precipitation of the composition wherethe product is negatively impacted aesthetically and/or functionally ina significant manner.

Exemplary hair styling polymers include the following:

a) Silicone-Containing Hair Styling Copolymers

Suitable hair styling polymers include graft and block copolymers ofsilicone with a nonsilicone adhesive polymer. Whether graft or block,these copolymers should satisfy the following four criteria:

(1) when dried the copolymer phase-separates into a discontinuous phasewhich includes the silicone portion and a continuous phase whichincludes the non-silicone portion;

(2) the silicone portion is covalently attached to the non-siliconeportion;

(3) the molecular weight of the silicone portion is from about 1,000 toabout 50,000; and

(4) the non-silicone portion must render the entire copolymer soluble ordispersible in the hair care composition vehicle and permit thecopolymer to deposit on/adhere to hair.

As used herein, phase separation is as described in U.S. Pat. No.5,658,557, Bolich et al., issued Aug. 19, 1997, hereby incorporated byreference.

The composition preferably contains from about 0.01% to about 20%, morepreferably from about 0.1% to about 15%, and most preferably from about1% to about 10% of the silicone containing hair styling polymer.

Suitable silicone copolymers include the following:

(i) Silicone Graft Copolymers

Preferred silicone polymers are the silicone graft copolymers described,along with methods of making them, in U.S. Pat. No. 5,658,557, Bolich etal., issued Aug. 19, 1997, U.S. Pat. No. 4,693,935, Mazurek, issued Sep.15, 1987, and U.S. Pat. No. 4,728,571, Clemens et al., issued Mar. 1,1988, each incorporated herein by reference. These silicone-containingcopolymers, provide hair conditioning and hair setting characteristicsto the composition.

These polymers include copolymers having a molecular weight of fromabout 10,000 to about 1,000,000, which have a vinyl polymeric backbonehaving grafted to it monovalent siloxane polymeric moieties, thecopolymer comprising C monomers and components selected from the groupconsisting of A monomers, B monomers, and mixtures thereof. A is atleast one free radically polymerizable vinyl monomer, and the amount byweight of A monomer, when used, is up to about 98% of the total weightof all monomers in the copolymer. B is at least one reinforcing monomercopolymerizable with A, and the amount by weight of B monomer, whenused, is up to about 98% of the total weight of all monomers in thecopolymer. The B monomer is selected from the group consisting of polarmonomers and macromers, preferably having a Tg or a T_(m) above about-20° C. C comprises from about 0.01% to about 50% of the copolymer andis a polymeric monomer having a molecular weight of from about 1,000 toabout 50,000 and the general formula

    X(Y).sub.n Si(R).sub.3-m (Z).sub.m

wherein

X is a vinyl group copolymerizable with the A and B monomers

Y is a divalent linking group

R is a hydrogen, lower alkyl (preferably C₁ -C₅, more preferably C₁-C₃), aryl or alkoxy

Z is a monovalent siloxane polymeric moiety having a number averagemolecular weight of at least about 500, is essentially unreactive undercopolymerization conditions, and is pendant from the vinyl polymericbackbone after copolymerization

n is 0or 1, and

m is an integer from 1 to 3.

In another embodiment, the silicone-containing copolymer has a vinylpolymeric backbone, preferably having a T_(g) above about -20° C., andgrafted to the backbone a polydimethylsiloxane macromer having a weightaverage molecular weight between about 1,000 and about 50,000,preferably from about 5,000 to about 40,000, most preferably about20,000, wherein the polymer is selected for a given composition suchthat, when dried, the polymer phase separates into a discontinuous phasewhich includes the polydimethylsiloxane macromer and a continuous phasewhich includes the backbone.

The polymers should have a weight average molecular weight of from about10,000 to about 1,000,000 (preferably from about 30,000 to about300,000) and, preferably, have a T_(g) of at least about 20° C. As usedherein in reference to these polymers, the abbreviation "T_(g) " refersto the glass transition temperature of the non-silicone backbone, andthe abbreviation "T_(m) " refers to the crystalline melting point of thenon-silicone backbone, if such a transition exists for a given polymer.

Representative examples of A (hydrophobic) monomers are acrylic ormethacrylic acid esters of C₁ -C₁₈ alcohols, such as methanol, ethanol,methoxy ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol,2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol(2-methyl-2-propanol), cyclohexanol, neodecanol,2-ethyl-1-butanol, 3-heptanol, benzyl alcohol, 2-octanol,6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, 1-hexadecanol,1-octadecanol, and the like, the alcohols having from about 1-18 carbonatoms with the average number of carbon atoms being from about 4-12;styrene; polystyrene macromer; vinyl acetate; vinyl chloride; vinylidenechloride; vinyl propionate; alpha-methylstyrene; t-butylstyrene;butadiene; cyclohexadiene; ethylene; propylene; vinyl toluene; andmixtures thereof. Preferred A monomers include n-butyl methacrylate,isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate,2-ethylhexyl methacrylate, methyl methacrylate, and mixtures thereof.

Representative examples of B monomers (hydrophilic) include acrylicacid, methacrylic acid, N,N-dimethylacrylamide, dimethylaminoethylmethacrylate, quaternized dimethylaminoethyl methacrylate,methacrylamide, N-t-butyl acrylamide, maleic acid, maleic anhydride andits half esters, crotonic acid, itaconic acid, acrylamide, acrylatealcohols, hydroxyethyl methacrylate, diallyldimethyl ammonium chloride,vinyl pyrrolidone, vinyl ethers (such as methyl vinyl ether),maleimides, vinyl pyridine, vinyl imidazole, other polar vinylheterocyclics, styrene sulfonate, allyl alcohol, vinyl alcohol (producedby the hydrolysis of vinyl acetate after polymerization) vinylcaprolactam, and mixtures thereof. Preferred B monomers include acrylicacid, N,N-dimethylacrylamide, dimethylaminoethyl methacrylate,quaternized dimethylaminoethyl methacrylate, vinyl pyrrolidone, andmixtures thereof.

Preferably, the C monomer has a formula selected from the followinggroup: ##STR1##

In those structures, m is 1, 2 or 3 (preferably m=1); p is 0 or 1,preferably 0; R" is alkyl or hydrogen; q in all but (IV) is an integerfrom 2 to 6, in (IV) q is an integer of from 0 to 6; X is ##STR2## R¹ ishydrogen or --COOH; R² is hydrogen, methyl or --CH₂ COOH; Z is ##STR3##R4 is alkyl, alkoxy, alkylamino, aryl, or hydroxyl (preferably R4 isalkyl); and r is an integer from about 5 to about 700.

The silicone graft polymers generally comprise from 0% to about 98%(preferably from about 5% to about 98%, more preferably from about 20%to about 90%) of monomer A, from about 0% to about 98% (preferably fromabout 7.5% to about 80%) of monomer B, and from about 0.1% to about 50%(preferably from about 0.5% to about 40%, most preferably from about 2%to about 25%) of monomer C. The combination of the A and B monomerspreferably comprises from about 50.0% to about 99.9% (more preferablyabout 60% to about 99%, most preferably from about 75% to about 95%) ofthe polymer. The composition of any particular copolymer will helpdetermine its formulational properties. In fact, by appropriateselection and combination of particular A, B and C components, thecopolymer can be optimized for inclusion in specific vehicles. Forexample, polymers which are soluble or micro-dispersible in an aqueousformulation preferably have the composition: from about 0% to about 70%(preferably from about 5% to about 70%) monomer A, from about 10% toabout 98% (preferably from about 10% to about 80%, more preferably fromabout 10% to about 60%) monomer B, and from about 1% to about 40%monomer C.

Particularly preferred polymers for use in the present invention includethe following (the weight percents below refer to the amount ofreactants added in the polymerization reaction, not necessarily theamount in the finished polymer):

acrylic acid/n-butylmethacrylate/(polydimethylsiloxane (PDMS)macromer--20,000 molecular weight) (10/70/20 w/w/w) (polymer molecularweight=200M)

N,N-dimethylacrylamide/isobutyl methacrylate/(PDMS macromer--20,000molecular weight) (20/60/20 w/w/w)(polymer molecular weight=50-300M)

N,N-dimethylacrylamide/(PDMS macromer--20,000 molecular wt) (80/20w/w)(polymer molecular weight=50-500M)

t-butylacrylate/acrylic acid/(PDMS macromer--12,000-14,000 molecular wt)(60/20/20 w/w/w)(polymer molecular weight=120-150M)

t-butylacrylate/acrylic acid/(PDMS macromer--12,000-14,000 molecular wt)(65/25/10 w/w/w)(polymer molecular weight=100-140M)

t-butylacrylate/acrylic acid/(PDMS macromer--10,000-15,000 molecular wt)(60/20/20 w/w/w)(polymer molecular weight=50-160M)

t-butylacrylate/methacrylic acid/(PDMS macromer--12,000-14,000 molecularwt) (60/20/20 w/w/w)(polymer molecular weight=50-160M)

t-butylacrylate/acrylic acid/(PDMS macromer--2,000-5,000 molecular wt)(60/20/20 w/w/w)(polymer molecular weight=50-150M) quaternizeddimethylaminoethyl methacrylate/isobutyl methacrylate/(PDMSmacromer--10,000-15,000 molecular wt) (60/20/20 w/w/w)(polymer molecularweight=90-120 M)

(ii) Silicone Block Copolymers

Also useful herein are silicone block copolymers comprising repeatingblock units of polysiloxanes.

Examples of silicone-containing block copolymers are found in U.S. Pat.No. 5,523,365, to Geck et al., issued Jun. 4, 1996; U.S. Pat. No.4,689,289, to Crivello, issued Aug. 25, 1987; U.S. Pat. No. 4,584,356,to Crivello, issued Apr. 22, 1986; Macromolecular Design, Concept &Practice, Ed: M. K. Mishra, Polymer Frontiers International, Inc.,Hopewell Jct., New York (1994), and Block Copolymers, A. Noshay and J.E. McGrath, Academic Press, New York (1977), which are all incorporatedby reference herein in their entirety. Other silicone block copolymerssuitable for use herein are those described, along with methods ofmaking them, in the above referenced and incorporated U.S. Pat. No.5,658,577.

The silicone-containing block copolymers useful in the present inventioncan be described by the formulas A--B, A--B--A, and --(A--B)_(n) --wherein n is an integer of 2 or greater. A--B represents a diblockstructure, A--B--A represents a triblock structure, and --(A--B)_(n) --represents a multiblock structure. The block copolymers can comprisemixtures of diblocks, triblocks, and higher multiblock combinations aswell as small amounts of homopolymers.

The silicone block portion, B, can be represented by the followingpolymeric structure

    --(SiR.sub.2 O).sub.m --,

wherein each R is independently selected from the group consisting ofhydrogen, hydroxyl, C₁ -C₆ alkyl, C₁ -C₆ alkoxy, C₂ -C₆ alkylamino,styryl, phenyl, C₁ -C₆ alkyl or alkoxy-substituted phenyl, preferablywherein R is methyl. In the preceding formula, m is an integer of about10 or greater, m is an integer of about 40 or greater, more preferablyof about 60 or greater, and most preferably of about 100 or greater.

The nonsilicone block, A, comprises monomers selected from the monomersas described above in reference to the A and B monomers for the siliconegrafted copolymers. The block copolymers preferably contain up to about50% (preferably from about 10% to about 20%) by weight of one or morepolydimethyl siloxane blocks and one or more non-silicone blocks(preferably acrylates or vinyls).

(iii) Sulfur-Linked Silicone Containing Copolymers

Also useful herein are sulfur-linked silicone containing copolymers,including block copolymers. As used herein in reference to siliconecontaining copolymers, the term "sulfur-linked" means that the copolymercontains a sulfur linkage (i.e., --S--), a disulfide linkage (i.e.,--S--S--), or a sulfhydryl group (i.e.,--SH).

These sulfur-linked silicone containing copolymers are represented bythe following general formula: ##STR4## wherein

G₅ independently represents monovalent moieties which can independentlybe the same or different selected from the group consisting of alkyl,aryl, alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and --ZSA; Arepresents a vinyl polymeric segment consisting essentially ofpolymerized free radically polymerizable monomer, and Z is a divalentlinking group. Useful divalent linking groups Z include but are notlimited to the following: C₁ to C₁₀ alkylene, alkarylene, arylene, andalkoxyalkylene. Preferably, Z is selected from the group consisting ofmethylene and propylene for reasons of commercial availability.

G₆ represents monovalent moieties which can independently by the same ordifferent selected from the group consisting of alkyl, aryl, alkaryl,alkoxy, alkylamino, fluoroalkyl, hydrogen, and --ZSA.

G₂ comprises A.

G₄ comprises A.

R₁ represents monovalent moieties which can independently be the same ordifferent and are selected from the group consisting of alkyl, aryl,alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl.Preferably, R₁ represents monovalent moieties which can independently bethe same or different selected from the group consisting of C₁₋₄ alkyland hydroxyl for reasons of commercial availability. Most preferably, R₁is methyl.

R₂ can independently be the same or different and represents divalentlinking groups. Suitable divalent linking groups include but are notlimited to the following: C₁ to C₁₀ alkylene, arylene, alkarylene, andalkoxyalkylene. Preferably, R₂ is selected from the group consisting ofC₁₋₃ alkylene and C₇ -C₁ alkarylene due to ease of synthesis of thecompound. Most preferably, R₂ is selected from the group consisting of--CH₂ --, 1,3-propylene, and ##STR5##

R₃ represents monovalent moieties which can independently be the same ordifferent and are selected from the group consisting of alkyl, aryl,alkaryl, alkoxy, alkylamino, fluoroalkyl, hydrogen, and hydroxyl.Preferably, R₃ represents monovalent moieties which can independently bethe same or different selected from the group consisting of C₁₋₄ alkyland hydroxyl for reasons of commercial availability. Most preferably, R₃is methyl.

R₄ can independently be the same or different and represents divalentlinking groups. Suitable divalent linking groups include but are notlimited to the following: C₁ to C₁₀ alkylene, arylene, alkarylene, andalkoxyalkylene. Preferably, R₄ is selected from the group consisting ofC₁₋₃ alkylene and C₇ -C₁ alkarylene for ease of synthesis. Mostpreferably, R₄ is selected from the group consisting of --H₂ --,1,3-propylene, and ##STR6## x is an integer of 0-3; y is an integer of 5or greater; preferably y is an integer ranging from about 14 to about700, preferably from about 100 to about 170;

q is an integer of 0-3; wherein at least one of the following is true:

q is an integer of at least 1;

x is an integer of at least 1;

G₅ comprises at least one--ZSA moiety;

G₆ comprises at least one--ZSA moiety.

As noted above, A is a vinyl polymeric segment formed from polymerizedfree radically polymerizable monomers. The selection of A is typicallybased upon the intended uses of the composition, and the properties thecopolymer must possess in order to accomplish its intended purpose. If Acomprises a block in the case of block copolymers, a polymer having ABand ABA architecture will be obtained depending upon whether a mercaptofunctional group --SH is attached to one or both terminal silicon atomsof the mercapto functional silicone compounds, respectively. The weightratio of vinyl polymer block or segment, to silicone segment of thecopolymer can vary. The preferred copolymers are those wherein theweight ratio of vinyl polymer segment to silicone segment ranges fromabout 98:2 to 50:50, in order that the copolymer possesses propertiesinherent to each of the different polymeric segments while retaining theoverall polymer's solubility.

Sulfur linked silicone copolymers are described in more detail in U.S.Pat. No. 5,468,477, to Kumar et al., issued Nov. 21, 1995, and PCTApplication No. WO 95/03776, assigned to 3M, published Feb. 9, 1995,which are incorporated by reference herein in their entirety.

b) Non-Silicone-Containing Hair Styling Polymers

The compositions of the present invention may alternatively oradditionally comprise a non-silicone-containing hair styling polymer.Non-silicone-containing hair styling polymers include nonionic, anionic,cationic, and amphoteric polymers, and mixtures thereof When used, thenon-silicone-containing hair styling polymers are preferably present ina combined amount of from about 0.01% to about 20%, more preferably fromabout 0.1% to about 15%, and most preferably from about 0.5% to about10% by weight of composition.

Suitable cationic polymers include Polyquaternium-4 (Celquat H-100;L200--supplier National Starch); Polyquaternium-10 (Celquat SC-240C;SC-230 M--supplier National Starch); (UCARE polymer series--JR-125,JR-400, LR-400, LR-30M, LK, supplier Amerchol); Polyquaternium-11(Gafquat 734; 755N--supplier ISP); Polyquaternium-16 (Luviquat FC 370;FC550; FC905; HM-552 supplier by BASF);PVP/Dimethylaminoethylmethacrylate (Copolymer 845; 937; 958--ISPsupplier); Vinyl Caprolactam/PVP/Dimethylaminoethyl Methacrylatecopolymer (Gaffix VC-713; H2OLD EP-1--supplier ISP); Chitosan (KytamerL; Kytamer PC--supplier Amerchol); Polyquaternium-7 (Merquat550--supplier Calgon); Polyquaternium-18 (Mirapol AZ-1 supplied byRhone-Poulenc); Polyquaternium-24 (Quatrisoft Polymer LM-200--supplierAmerchol); Polyquaternium-28 (Gafquat HS-100--supplier ISP);Polyquaternium-46 (Luviquat Hold--supplier BASF); and Chitosan Glycolate(Hydagen CMF; CMFP--supplier Henkel); Hydroxyethyl CetyldimoniumPhosphate (Luviquat Mono CP--supplier BASF); and Guar HydroxylpropylTrimonium Chloride (Jaguar C series -13S, -14S, -17, 162,-2000, Hi-CARE1000--supplier Rhone-Poulenc).

Preferred cationic polymers are Polyquaternium-4; Polyquaternium-10;Polyquaternium-11; Polyquaternium-16;PVP/Dimethylaminoethylmethacrylate; VinylCaprolactam/PVP/Dimethylaminoethyl Methacrylate copolymer; and Chitosan.

Suitable amphoteric polymers includeOctylacrylmide/Acrylates/Butylaminoethyl Methacrylate Copolymer(Amphomer 28-4910, Amphomer LV-71 28-4971, Lovocryl-47 28-4947--NationalStarch supplier), and Methacryloyl ethyl betaine/methacrylates copolymer(Diaformer series supplier Mitsubishi). Preferred areOctylacrylmide/Acrylates/Butylaminoethyl Methacrylate Copolymer.

Especially preferred polymers for relatively low alcohol systems, e.g.,less than about 55% alcohol, are those which are partially zwitterionicin that they always possess a positive charge over a broad range of pHbut contain acidic groups which are only negatively charged at basic pH.Therefore the polymer is positively charged at lower pH and neutral(have both negative and positive charge) at higher pHs. Zwitterionicpolymers useful herein include Polyquaternium-47 (Merquat 2001--supplierCalgon); Carboxyl Butyl Chitosan (Chitolam NB/101--marketed by PilotChemical Company, developed by Lamberti); and Dicarboxyethyl Chitosanavailable from Amerchol as an experimental sample.

Useful nonionic polymers include PVP or Polyvinylpyrrolidone (PVP K-15,K-30, K-60, K-90, K-120--supplier ISP) (Luviskol K series 12, 17, 30,60, 80, & 90--supplier BASF); PVP/VA (PVP/VA series S-630; 735, 635,535, 335, 235--supplier ISP )(Luviskol VA); PVP/DMAPA acrylatescopolymer (Styleze CC-10--supplier ISP); PVP/VA/Vinyl Propionatecopolymer (Luviskol VAP 343 E, VAP 343 I, VAP 343PM--supplier BASF);Hydroxylethyl Cellulose (Cellosize HEC--supplier Amerchol); andHydroxylpropyl Guar Gum (Jaguar HP series -8, -60, -105, -120--supplierRhone-Poulenc).

Preferred nonionic polymers are PVP or Polyvinylpyrrolidone; PVP/VA;PVP/DMAPA acrylates copolymer; and Hydroxylpropyl Guar Gum.

Anionic polymers suitable for use herein include VA/Crotonates/VinylNeodecanonate Copolymer (Resyn 28-2930--National Starch supplier); ButylEster of PVM/MA (Gantrez A-425; ES-425; ES-435--supplier ISP); EthylEster of PVM/MA (Gantrez ES-225; SP-215--supplier ISP);Acrylates/acrylamide copolymer (Luvimer 100P; Lumiver Low VOC, supplierBASF); Methacrylate Copolymer (Balance 0/55--National Starch supplier);Vinyl Acetate/Crotonic Acid copolymer (Luviset CA 66--supplier BASF);Isopropyl Ester of PVM/MA Copolymer (Gantrez ES-335--supplier ISP);Acrylates Copolymer; Methacrylates/acrylates copolymer/amine salt(Diahold polymers--supplier Mitsubishi); 2-Butenedioic Acid (Z)--,Monoethyl Ester, Polymer with Methoxyethene (Omnirez 2000); VA/Butylmaleate/Isobornyl Acrylate (Advantage Plus terpolymer--supplier ISP);Acrylates Copolymer (Amerhold DR-25--supplier Amerchol);Acrylates/Hydroxyesteracrylates Copolymer (Acudyne 255 supplier Rohm &Haas); vinyl Acetate/Crotonic Acid/Vinyl Propionate copolymer (LuvisetCAP--supplier BASF); PVP/Acrylates copolymer (Luviflex VBM 35--supplierBASF); Diglycol/CHDM/Isophthalates/SIP Copolymer (Eastman AQ 48, AQ55--supplier Eastman Chemicals); Acrylates/Octacrylamide Copolymer(Versatyl-42 or Amphomer HC--National Starch supplier); TBA/AA copolymer(75/25--Mitsubishi Chemical Corp.); and Carbomer (supplier B.F.Goodrich).

Preferred anionic polymers are VA/Crotonates/Vinyl NeodecanonateCopolymer; Butyl Ester of PVM/MA; Ethyl Ester of PVM/MA;Acrylates/acrylamide copolymer; Methacrylate Copolymer; and VinylAcetate/Crotonic Acid copolymer.

Carrier

The compositions of the invention also comprise a carrier for theessential and optional components. Suitable carriers are those in whichthe hair styling polymer is soluble or dispersible, preferably solubleor microdispersible. Choice of an appropriate carrier will also dependon the particular end use and product form contemplated (e.g., the hairstyling polymer to be used, and the product form, e.g., for hair stylingcompositions such as hair spray, mousse, tonic, lotion or gel).Preferred carriers are those which are suitable for application to thehair.

The carrier is present at from about 0.5% to about 99.5%, preferablyfrom about 5% to about 99.5%, most preferably from about 50% to about95%, of the composition.

The compositions of the present invention comprise one or more suitablesolvents. Preferred solvent systems are those which form a homogeneoussolution or dispersion (preferably microdispersion) with the essentialcomponents in the weight ratios used in the composition. Preferredsolvent systems are those which form a substantially clear totranslucent solution or dispersion (preferably microdispersion) with theessential components in the weight ratios used in the composition.

Preferred solvents include those selected from the group consisting ofwater; water soluble organic solvents; organic solvents which arestrongly to moderately strong in hydrogen-bonding parameter; andmixtures thereof; wherein the solvent is other than C₁ -C₃ monohydricalcohol, C₁ -C₃ ketone and C₁ -C₃ ether. Water is a preferred solvent.At least about 0.5%, preferably at least about 1%, of this type ofsolvent is used in the composition.

Exemplary water soluble organic solvents other than C₁ -C₃ monohydricalcohols, ketones and ethers include propylene glycol, glycerine,phenoxyethanol, dipropylene glycol, sugars, and mixtures thereof.

Solvents which are moderately strong to strong in hydrogen-bondingparameter other than C₁ -C₃ monohydric alcohols, ketones and ethersinclude esters, ethers, ketones, glycol monoethers (moderately H-bonded)and alcohols, amines, acids, amides and aldehydes (strongly H-bonded). Adescription and examples of solvents of this type are disclosed inPolymer Handbook, 2d. Ed., J. Brandrup and E. H. Immergut, Editors, JohnWiley & Sons, New York, 1975, Section IV, page 337-348 (Table 2).Preferred solvents of this type are dibutyl phthalate, propylenecarbonate, propylene glycol monomethyl ether, methyl acetate, methylproprionate and mixtures thereof Propylene glycol monomethyl ether,methyl acetate, methyl proprionate and mixtures thereof are preferred;methyl acetate is most preferred.

Other solvents suitable for use herein are water soluble, organicvolatile solvents selected from C₁ -C₃ monohydric alcohols, C₁ -C₃ketones, C₁ -C₃ ethers, and mixtures thereof, monohydric alcohols beingpreferred. Preferred solvents of this type are methylal, ethanol,n-propanol, isopropanol, acetone and mixtures thereof More preferred areethanol, n-propanol, isopropanol, and mixtures thereof.

In a preferred embodiment, the carrier comprises (i) a solvent selectedfrom the group consisting of water; water soluble organic solvents;organic solvents which are strongly to moderately strong inhydrogen-bonding parameter; and mixtures thereof; wherein the solvent isother than C₁ -C₃ monohydric alcohol, C₁ -C₃ ketone and C₁ -C₃ ether;(ii) a solvent selected from the groups consisting of C₁ -C₃ monohydricalcohols, C₁ -C₃ ketones, C₁ -C₃ ethers, and mixtures thereof; and (iii)mixtures thereof, preferably a mixture thereof. Especially preferred area mixture of water and C₁ -C₃ monohydric alcohol, e.g., water-ethanol orwater-isopropanol-ethanol. Another particularly preferred solvent systemcomprises one or more of propylene glycol monomethyl ether, methylacetate, and methyl proprionate, preferably methyl acetate, optionallywith one or more of water or a C₁ -C₃ monohydric alcohol.

The carrier may include other solvents, e.g., hydrocarbons (such asisobutane, hexane, decene, acetone), halogenated hydrocarbons (such asFreon), linalool, volatile silicon derivatives, especially siloxanes(such as phenyl pentamethyl disiloxane, methoxypropyl heptamethylcyclotetrasiloxane, chloropropyl pentamethyl disiloxane, hydroxypropylpentamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane), and mixtures thereof.

Solvents used in admixture may be miscible or immiscible with eachother. However, in the final composition such solvents should becompatible with each other and other components in the composition suchthat solids do not precipitate.

Reduced "volatile organic compound" or "VOC" compositions may bedesirable. In this regard, "VOC" refers to those organic compounds thatcontain less than 12 carbon atoms or have a vapor pressure greater thanabout 0.1 mm of mercury. For example, the composition may have, asinitially applied, a total VOC content of about 95% or less, about 80%or less, about 55% or less (e.g., in preferred hairsprays), about 16% orless (e.g., in preferred mousses), or about 6% or less (e.g., inpreferred gels). The VOC may be based on actual VOC content, or the VOCwhich is delivered upon initial dispensing from a package.

Where the composition comprises a silicone graft hair styling copolymer,the compositions hereof may contain a volatile, nonpolar, branched chainhydrocarbon, which acts as a solvent for the silicone portion of thesilicone grafted copolymer. When used, the branched chain hydrocarbonsolvent hereof is present at a level of from about 0.01% to about 15%,preferably from about 0.05% to about 10%, more preferably from about0.1% to about 8%, by weight of the composition.

The branched chain hydrocarbon solvent is characterized by a boilingpoint of at least about 105° C., preferably at least about 110° C., morepreferably at least about 125° C., most preferably at least about 150°C. The boiling point is also generally about 260° C. or less, preferablyabout 200° C. or less. The hydrocarbon chosen should also be safe fortopical application to the hair and skin.

The branched chain hydrocarbon solvents are described in detail in U.S.Pat. No. 5,565,193 and are hereby incorporated by reference. The solventincludes those selected from the group consisting of C₁₀ -C₁₄ branchedchain hydrocarbons, and mixtures thereof, preferably C₁₁ -C₁₃ branchedchain hydrocarbons, more preferably C₁₂ branched chain hydrocarbons.Saturated hydrocarbons are preferred, although it isn't necessarilyintended to exclude unsaturated hydrocarbons.

Examples of suitable nonpolar solvents include isoparaffins of the abovechain sizes. Isoparaffins are commercially available from Exxon ChemicalCo. Examples include Isopar™ G (C₁₀ -C₁₁ isoparaffins), Isopar™ H and K(C₁₁ -C₁₂ isoparaffins), and Isopar™ L (C₁₁ -C₁₃ isoparaffins). The mostpreferred nonpolar solvent are C₁₂ branched chain hydrocarbons,especially isododecane. Isododecane is commercially available fromPreperse, Inc. (South Plainfield, N.J., U.S.A) as Permethyl™ 99A.

The solubility of the silicone portion of the hair styling polymer canbe easily determined by verifying whether a silicone polymer of the samecomposition and molecular weight as that in the hair styling polymer issoluble in the nonpolar hydrocarbon solvent. In general, the siliconepolymer should be soluble at 25° C. at a concentration of 0.1% by weightof the hydrocarbon solvent, preferably at 1%, more preferably at 5%,most preferably at 15%.

The nonpolar hydrocarbon solvent, however, is insoluble in the polarsolvents of the composition. This is determined in the absence of thehair styling polymer, or other emulsifying agents, and can easily beverified by observing whether the polar and nonpolar solvents formseparate phases after being mixed together.

Without intending to be necessarily limited by any particular theory, itis believed that the nonpolar hydrocarbon solvent solubilizes thesilicone portion of the hair styling polymer. This is believed to aid inobtaining a smoother, more lubricious polymer film upon drying.

The carrier may also comprise conventional components such as are knownin the art suitable for a given product form.

Properties of Hair Styling Compositions

The hair styling compositions of the present invention exhibit specificphysical properties as defined by the Stiffness Value (SV) and CurlRetention Index (CRI) which are determined as described below.

Compositions of the invention are characterized by having an SV and CRIrelated as follows:

    SV≧[(0.703×CRI)-0.425].

Preferred compositions are characterized by having an SV and CRI relatedas follows:

    SV≧[(0.703×CRI)-0.80].

More preferred compositions are characterized by having a SV and CRIrelated as follows:

    SV≧[(0.703×CRI)-1.55].

Methodology for determining SV and CRI

The following applies in determining each value. The hair switches aremade by Advanced Testing Laboratories (Cincinnati, Ohio). Also, theshampoo referred to herein contains the following:

    ______________________________________                                        Shampoo composition                                                           Component          Weight %                                                   ______________________________________                                        Ammonium AE3 Sulfate                                                                             51.24                                                      Ammonium Lauryl Sulfate                                                                          36.38                                                      Cocamide DEA       2.30                                                       Ammonium Xylenesulfonate                                                                         3.50                                                       Perfume            0.50                                                       Water              q.s.                                                       ______________________________________                                    

Additionally, all water is 100° F. tap water with a grain of 7 to 11 anda flow rate of 1.5 gpm. Also, care is taken to avoid contamination of agiven product with another (e.g., by wearing clean gloves). Furthermore,the procedures described below are considered valid only when they areaccurate and reproducible such that the standard deviation within a testis no greater than 0.75 (7.5% of the total test scale).

a) Stiffness Value

The Stiffness Value (SV) of a treated hair switch can be determined byhaving panelists rank hair treated switches for stiffness on a scale of0 to 10 where 0 is untreated hair and 10 is very stiff.

The hair switches used in the procedure are 20 gm/10" long, flat,permed, and bleached. A sufficient number of switches are permed andbleached such that there are 2 switches per test product and 4 switchesper control. Perming is necessary to remove any natural wave in the hairwhich could interfere with measuring the performance of products appliedto the hair. The perm treatment involves rinsing each switch with waterfor 30 seconds. The switch is blotted dry and hung vertically. 20 cc ofPerfect Comb Out Perm waving solution (commercially available from ZOTOSInternational, Inc., Darien, Conn.) is applied to the switch. After theswitch is combed through, an additional 5 cc of waving solution isapplied. The solution is permitted to remain on the switch for 60minutes. After an hour, the switch is rinsed with water for 1 minute andblotted dry. 20 cc of Perfect Comb Out Neutralizer (ZOTOS) is thenapplied to each switch and combed through. An additional 5cc ofneutralizer is applied and remains on the switch for 5 minutes.Afterwards, the switch is rinsed with water for 1 minute and hung todry.

Bleaching, like perming, serves to further damage the hair switches.This procedure involves bleaching 3 switches at a time. First, foil isspread on a flat surface on which the switches are then laid. The bleachmixture is prepared by weighing 55 gms of powdered bleach (18.3gms/switch) into a large glass beaker. Then, 225 ml of liquid peroxideor developer (75ml/switch) is slowly added to the powdered bleach. Themixture is stirred slowly and carefully. Once all the powder is wet, themixture may be stirred vigorously until well blended.

The bleach mixture is applied to the switches by pouring about 25 ml oneach switch in a zig-zag pattern. Once the switch is quickly coveredwith the bleach mixture, the top of the switch is held securely againstthe foil with one hand while the bleach is massaged through the switchwith the other hand. Then, the switch is quickly turned over and thebleach application process is repeated. Once the second massage iscomplete, the bleached switch is allowed to set for 12 minutes. Thebleaching application process should be repeated for each of the tworemaining switches as quickly as possible to ensure that each switch isprocessed for approximately the same time. If the application processtakes more than a couple of minutes, each switch should be individuallytimed so that the variability from switch to switch is minimal.

Once the 12 minute processing time is over, each switch is immediatelyhung and rinsed thoroughly with water for 1 minute. The switches shouldbe rinsed in the same order in which they were treated. The switches arethen cleaned with 2 lather cycles of 0.4 cc of shampoo where theswitches are lathered for 30 seconds and rinsed for 30 seconds. Sincethe switches are very fragile immediately after bleaching, each switchis gently combed to remove any tangles during the second lather cycle.After the second rinse, the switches are hung to dry.

Two controls (0 and 10) are required in order to determine the StiffnessValue of the test products. The 0 control is an untreated,shampooed-only hair switch. The 10 control is a hair switch that istreated with a composition prepared by mixing the components listedbelow:

    ______________________________________                                        10 Control treatment composition:                                             Component        Weight %                                                     ______________________________________                                        Water            96.18                                                        Polyquaternium-4.sup.1                                                                         3.00                                                         Isosteareth-20.sup.2                                                                           0.50                                                         Benzophenone-4   0.10                                                         Tetrasodium EDTA 0.10                                                         Perfume          0.12                                                         ______________________________________                                         .sup.1 Celquat H100; National Starch                                          .sup.2 Arosurf 66 E20, Witco                                             

In preparation for product application, the switches are randomly hungsuch that the entire 10" length of each switch is exposed. Each switchis then rinsed with water for 15 seconds. After rinsing, the excesswater is squeezed from each switch by running the thumb and index fingeralong the length of the switch with firm pressure three times. 1 cc ofshampoo is applied to each switch and is massaged therein for 30 secondssuch that the shampoo is distributed evenly throughout the switch. Eachswitch is rinsed with water for 60 seconds and squeezed twice asdescribed above.

Next, in ambient laboratory conditions, the various test products aswell as the 10 control composition are applied to the hair switches. Forgel compositions, 1 cc of gel is applied to each switch in a repeating"S" pattern from the top of the switch down its entire length. For 30seconds, the product is milked throughout each switch by twisting theswitch back and forth to ensure even distribution of the gel throughoutthe switch. For mousse compositions, 1 gm of mousse is dispensed and 1/2gm is applied to each side of each of the switches. The mousse is thenmilked throughout each switch for 30 seconds as explained above. Next,each switch is combed through twice with a wide tooth detangling comb.The switches are lightly squeezed as described above such that theswitches resemble flat ribbons. The hanging switches are placed into a73° F./50% R.H. room overnight to dry and equilibrate.

After about 12 hours of drying, the treated switches are divided into 2sets and randomized in preparation for tactile analysis bypanelists/graders. One set of controls is identified for the panelistsand positioned near the test product switches as reference anchors whilethe other set of controls are randomly mixed among the set of testproduct switches. Each set of test switches comprises one switch perproduct/control composition. The switches are combed through twice witha wide tooth, detangling comb. The panelists cleanse their fingertipswith isopropyl alcohol swabs and allow them to dry prior to ranking eachswitch. A minimum of 5 panelists rank each set of switches on thesensory stiffness scale. The tactile stiffness rank of each switch isdetermined by the panelist by touching the switch with bare fingers andranking its stiffness on the above described stiffness scale of 0 to 10.The mean stiffness rank of a test product is determined by averaging thestiffness rank of each switch to which the same test product wasapplied. The mean stiffness rank referred to as the Stiffness Value (SV)of a given product.

b) Curl Retention Index

The Curl Retention Index is predictive of perceived style/hold benefitsin gels and mousse by measuring the amount of curl retention over time.The curl retention of a test product is compared and indexed to that ofcontrol products. For testing of gel and mousse compositions, thefollowing 3 control products are used: 1) low hold control--untreated(assigned a value of 0) and 2) high hold control--detailed below(assigned a value of 10).

The control product has the following formulation:

    ______________________________________                                        10 Control Treatment Composition:                                             Component          Weight %                                                   ______________________________________                                        Water              81.33                                                      Polyquat-11 (20% active).sup.1                                                                   15.00                                                      Isosteareth 20.sup.2                                                                             0.50                                                       Perfume            0.20                                                       Diethylene Glycol  0.30                                                       Glycerin           0.25                                                       Hydroxypropyl Guar.sup.3                                                                         1.50                                                       Preservatives      0.92                                                       ______________________________________                                         .sup.1 Gafquat755N, ISP                                                       .sup.2 Arosurf 66 E20, Witco                                                  .sup.3 Jaguar HP105, RhonePoulenc                                        

The control composition is prepared in the following manner. A premix isprepared by completely dissolving the Polyquaternium-11 in 50% of thebatch water (130° F.) with vigorous agitation. Next, add the diethyleneglycol (DEG) and wait for dissolution of Polyquaternium-11 and the DEG.Under continued agitation, add the Isosteareth-20, the perfume, theglycerin, and the preservatives. The final mix is prepared undervigorous agitation by dissolving the hydroxypropyl guar in 50% of thebatch water (100° F.). With mild agitation, add the premix and stirwell.

Once the 10 control is made, the hair switches are prepared. Thisprocedure utilizes curly permed hair switches which are prepared in thefollowing manner. First, three to five-4 gm/8" long, round switches pertest product (including controls) are rinsed with water for 30 secondsand the excess water is squeezed from the switch using the first twofingers. Next, 0.5 cc of Perfect Comb Out waving lotion (ZOTOS) isapplied to the bottom 2" of each switch using a syringe. Each switch isthen divided into 3 equal sections. Once an end wrap is placed on theend of each section, each section is then curled by starting at theright side of a 3/8" straight rod, wrapping the hair tightly andspirally along the length of the rod. Using a syringe, 8 cc of wavinglotion is applied such that the entire switch is covered. The rolledswitches are then placed in plastic bag or wrapped in cellophane 2 at atime. After 30 minutes, the switches are unrolled and checked to see ifthe desired wave pattern has been achieved. If not, the switches arethen re-rolled and spot checked every 2 minutes until the desired wavepattern is achieved, being careful not to exceed a total of 45 minutes.With the rods still intact, the switches are then rinsed for 90 secondsand blotted with a paper towel to remove excess water. After blotdrying, 10 cc of 20 volume peroxide is applied to each rolled switch.Five minutes later the rods are removed from the :switches. The switchesare rinsed with water for 1 minute, and blotted with a paper towel.Without combing, the switches are then laid flat on a plexiglass trayand left to dry in a room at ambient temperature and relative humidity.After about 2 to 3 days, the switches are shampooed with 4 cc of shampooby lathering for 30 seconds, rinsing with water for 30 seconds,lathering for 30 more seconds, and rinsing with water again for 60seconds. Each switch is blotted three times with a paper towel.

Next, the various products and control compositions are applied to theswitches. For gel products, a total amount of 0.3 cc of gel is appliedwith the fingertips to the front and back of each switch. Each switch isthen milked thoroughly for 15 seconds to ensure even distribution of thegel throughout the switch. For mousses, a total amount of 0.2 gms ofmousse is applied to each switch, (0.1 gm on each side of each switch)and milked throughout as described above. Upon completion of productapplication, each switch is combed through once with a small toothbeautician's comb and the excess water is squeezed from each switch byrunning the thumb and forefinger along the length of each switch suchthat the hair resembles a smooth, flat ribbon.

Next, the hair of each switch is curled using a 22 mm diameter, 70 mmlong `magnetic` roller with a matching cover. The hair of each switch iscurled by starting at the right side of the roller and wrapping the hairtightly around the roller, catching the hair ends under the hair strandas the hair is rolled with tension spirally up the roller. It isimportant to use the same amount of tension when curling all switchsamples in order to ensure like test conditions. Once each switch isrolled, each roller is placed on end on a plexiglass tray in aconvection air drying box for 3 hours at approximately 135° F. to 140°F. and at an ambient relative humidity. Once drying is complete, thestill-rolled switches are placed in the 80° F./15% R.H. room and allowedto cool for about 30 minutes before the rollers are removed from theswitches.

After cooling, the rollers are removed by carefullying unrolling eachswitch. In preparation for curl fall measurements, each curled switch ishung vertically and grouped according to test product. The initiallength of the curled switch (L₀) is measured from the lowest end of theclip holding the switch to the end of the switch. This measurement istaken to the nearest mm using a metric ruler. The switches are thenplaced in a 80° F./80% R.H room and the curl lengths are remeasured at45 minutes (L₄₅) to determine the curl fall. The Curl Retention Value(CRV) for a switch is calculated using the following formula: ##EQU1##where L is the original length of the untreated switch; L₄₅ is thelength of the test product or control curl switch after 45 minutes; andL₀ is the length of the test product or control switch at the time ofroller removal. The mean of the curl retention values (CRV_(m)) iscalculated for each test product as well as for the 0 and 10 controls,by averaging the CRVs obtained for a given switch. The mean, CRV_(m) isthen used to calculate the Curl Retention Index (CRI) of a given productusing the following formula: ##EQU2## where CRV_(mp) =mean curlretention value of the test product;

CRV_(ml) =mean curl retention value of the of the 0 control; and

CRV_(mh) =mean curl retention value of the of the 10 control.

Optional Components

The present compositions can contain a wide variety of other optionalingredients that are suitable for application to human hair, includingamong them any of the types of ingredients known in the art for use inhair care compositions, especially hair setting compositions like hairspray compositions, mousses, gels and tonics. Preferred compositions ofthe present invention are mousses and gels. Generally, such otheradjuvants collectively comprise from about 0.05% to about 5% by weightand preferably from about 0.1% to about 3%, by weight of thecompositions. Such conventional optional adjuvants are well known tothose skilled in the art and include, but are not limited to,plasticizers, surfactants (which may be anionic, cationic, amphoteric ornonionic), neutralizing agents, propellants, hair conditioning agents(e.g., silicone fluids, fatty esters, fatty alcohols, long chainhydrocarbons, isobutene, cationic surfactants, etc.), emollients,lubricants and penetrants such as various lanolin compounds,preservatives, dyes, tints, bleaches, reducing agents and othercolorants, sunscreens, vitamins, proteins, thickening agents (e.g.,polymeric thickeners, such as xanthan gum) physiologically activecompounds for treating the hair or skin (e.g., anti-dandruff actives,hair growth actives), and perfume.

Non-exclusive examples of certain types of optional components areprovided below.

a) Plasticizers

The compositions hereof may contain a plasticizer for the hair stylingpolymer. Any plasticizer suitable for use in hair care products or fortopical application to the hair or skin can be used. A wide variety ofplasticizers are known in the art. These include glycerine, diisobutyladipate, butyl stearate, propylene glycol, diethylene glycol, otherglycols, tri-C₂ -C₈ alkyl citrates, including triethyl citrate andanalogs of triethyl citrate.

Plasticizers are typically used at levels of from about 0.01% to about200%, preferably from about 0.05% to about 100%, and more preferablyfrom about 0.1% to about 50% by weight of the polymer.

b) Surfactants

The hair styling compositions can contain one or more surfactants, e.g.,for emulsifying hydrophobic components which may be present in thecomposition. Surfactants are preferred for use in mousse products.Generally, if used such surfactants will be used at a total level offrom about 0.01% to about 10%, preferably from about 0.01% to about 5%and more preferably from about 0.01% to about 3%, by weight of thecomposition. A wide variety of surfactants can be used, includinganionic, cationic, amphoteric, and zwitterionic surfactants.

Anionic surfactants include, for example: alkyl and alkenyl sulfates;alkyl and alkenyl ethoxylated sulfates; (preferably having an averagedegree of ethoxylation of 1 to 10), succinamate surfactants, such asalkylsulfosuccinamates and dialkyl esters of sulfosuccinic acid;neutralized fatty acid esters of isethionic acid; and alkyl and alkenylsulfonates, including, for example, olefin sulfonates and beta-alkoxyalkane sulfonates. Preferred are alkyl and alkenyl sulfates and alkyland alkenyl ethoxylated sulfates such as the sodium and ammonium saltsof C₁₂ -C₁₈ sulfates and ethoxylated sulfates with a degree ofethoxylation of from 1 to about 6, preferably from 1 to about 4, e.g.,lauryl sulfate and laureth (3.0) sulfate.

Amphoteric surfactants include those which can be broadly described asderivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic water solubilizing group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples ofcompounds falling within this definition are sodium3-dodecylaminopropionate, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof U.S. Pat. No. 2,658,072, N-higher alkyl aspartic acids such as thoseproduced according to the teaching of U.S. Pat. No. 2,438,091, and theproducts sold under the trade name "Miranol" and described in U.S. Pat.No. 2,528,378. Others include alkyl, preferably C₆ -C₂₂ and mostpreferably C₈ -C_(12') amphoglycinates; alkyl, preferably C₆ -C₂₂ andmost preferably C₈ -C₁₂ ' amphopropionates; and mixtures thereof.

Suitable zwitterionic surfactants for use in the present compositionscan be exemplified by those which can be broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radicals can be straight chain orbranched, and wherein one of the aliphatic substituents contains fromabout 8 to 18 carbon atoms and one contains an anionicwater-solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate,or phosphonate. A general formula for these compounds is: ##STR7##wherein R2 contains an alkyl, alkenyl, or hydroxy alkyl radical of fromabout 8 to about 18 carbon atoms, from 0 to about 10 ethylene oxidemoieties and from 0 to 1 glyceryl moiety; Y is selected from the groupconsisting of nitrogen, phosphorus, and sulfur atoms; R3 is an alkyl ormonohydroxyalkyl group containing 1 to about 3 carbon atoms; x is 1 whenY is sulfur or phosphorus, 1 or 2 when Y is nitrogen; R4 is an alkyleneor hydroxyalkylene of from 1 to about 4 carbon atoms and Z is a radicalselected from the group consisting of carboxylate, sulfonate, sulfate,phosphonate, and phosphate groups. Classes of zwitterionics includealkyl amino sulfonates, alkyl betaines, and alkyl amido betaines.

Cationic surfactants useful in compositions of the present inventioncontain amino or quaternary ammonium hydrophilic moieties which arepositively charged when dissolved in the aqueous composition of thepresent invention. Cationic surfactants among those useful herein aredisclosed in the following documents, all incorporated by referenceherein: M. C. Publishing Co., McCutcheon's, Detergents & Emulsifiers,(North American edition 1979); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, New York: Interscience Publishers, 1949;U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678, Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Pat. No.4,387,090, Bolich, Jr., issued Jun. 7, 1983.

Among the quaternary ammonium-containing cationic surfactant materialsuseful herein are those of the general formula: ##STR8## wherein R₁ isan aliphatic group of from 1 to 22 carbon atoms, or an aromatic, aryl oralkylaryl group having from 12 to 22 carbon atoms; R₂ is an aliphaticgroup having from 1 to 22 carbon atoms; R₃ and R₄ are each alkyl groupshaving from 1 to 3 carbon atoms, and X is an anion selected fromhalogen, acetate, phosphate, nitrate and alkylsulfate radicals. Thealiphatic groups may contain, in addition to carbon and hydrogen atoms,ether linkages, and other groups such as amido groups. Other quaternaryammonium salts useful herein are diquaternary ammonium salts.

Salts of primary, secondary and tertiary fatty amines are also suitablecationic surfactants for use herein. The alkyl groups of such aminespreferably have from 12 to 22 carbon atoms, and may be substituted orunsubstituted. Secondary and tertiary amines are preferred, tertiaryamines are particularly preferred. Such amines, useful herein, includestearamido propyl dimethyl amine, diethyl amino ethyl stearamide,dimethyl stearamine, dimethyl soyamine, soyamine, myristyl amine,tridecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated(5 moles E.O.) stearylamine, dihydroxy ethyl stearylamine, andarachidyl-behenylamine. Cationic amine surfactants included among thoseuseful in the present invention are disclosed in U.S. Pat. No.4,275,055, Nachtigal, et al., issued Jun. 23, 1981 (incorporated byreference herein).

Suitable cationic surfactant salts include the halogen, acetate,phosphate, nitrate, citrate, lactate and alkyl sulfate salts.

Nonionic surfactants can also be included in the compositions hereof.Nonionic surfactants include polyethylene oxide condensates of alkylphenols (preferably C₆ -C₁₂ alkyl, with a degree of ethoxylation ofabout 1 to about 6), condensation products of ethylene oxide with thereaction product of propylene oxide and ethylene diamine, condensationproducts of aliphatic alcohols with ethylene oxide, long chain (i.e.,typically C₁₂ -C₂₂) tertiary amine oxides, long chain tertiary phosphineoxides, dialkyl sulfoxides containing one long chain alkyl or hydroxyalkyl radical and one short chain (preferably C₁ -C₃) radical, siliconecopolyols, and C₁ -C₄ alkanol amides of acids having a C₈ -C₂₂ acylmoiety. Preferred nonionic surfactants are C₁ -C₄ alkanol amides ofacids having a C₈ -C₂₂ acyl moiety, polyoxyethylene glycol stearylethers, and mixtures thereof. Specific examples which are preferred areLauramide DEA, Steareth-21, Steareth-2, and Na Cocoyl Isethionate.

Additional surfactants suitable for use herein include those describedin reference to the silicone microemulsion.

c) Neutralizing Agents

Hair styling polymers which have acidic functionalities, such ascarboxyl groups, are preferably used in at least partially neutralizedform to promote solubility/dispersibility of the polymer. In addition,use of the neutralized form aids in the ability of the dried hairstyling compositions to be removed from the hair by shampooing. Thedegree of neutralization must balance shampoo removability versushumidity resistance. Neutralization levels in excess of what is requiredfor shampoo removability will result in excessively sticky products thatwill not hold as well in high humidity. When available acidic monomersare neutralized, it is preferred that from about 5% to 60%, morepreferably from about 10% to about 40%, and even more preferably fromabout 12% to about 30% of the polymer (on a total polymer weight basis)be neutralized. The optimal level of neutralization for a specificpolymer will depend on the polarity of the monomers selected, thespecific ratios of the monomers to each other, and the percentage ofacidic monomers. The level of base needed to neutralize the acid groupsin a polymer for a specific % neutralization of the polymer may becalculated from the following equation: ##EQU3## A=% Polymer incomposition B=% of polymer to be neutralized (assuming acid groups areavailable)

C=MW of Base

D=MW of Acid monomer

Any conventionally used base, including organic or inorganic (metallicor other) bases, can be used for neutralization of the polymers.Metallic bases are particularly useful in the present compositions.Hydroxides, where the cation is ammonium, an alkali metal or an alkalineearth metal, are suitable neutralizers for use in the presentcompositions. Preferred inorganic neutralizing agents for use in thecompositions of the present invention are potassium hydroxide and sodiumhydroxide. Examples of other suitable neutralizing agents which may beincluded in the hair styling compositions of the present inventioninclude amines, especially amino alcohols such as2-amino-2-methyl-1,3-propanediol (AMPD), 2-amino-2-ethyl-1,3-propanediol(AEPD), 2-amino-2-methyl-1-propanol (AMP), 2-amino-1-butanol (AB),monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA),monoisopropanolamine (MIPA), diisopropanolamine (DIPA),triisopropanolamine (TIPA), dimethyl laurylamine (DML), dimethylmyristalamine (DMM) and dimethyl stearamine (DMS) For silicone graftedpolymers in compositions with water levels >30%, sodium hydroxide is themost preferred inorganic base; particularly useful amine neutralizingagents are dimethyl myristalamine, dimethyl laurylamine, and mixturesthereof.

Polymers having basic functionalities, e.g., amino groups, arepreferably at least partially neutralized with an acid, e.g.,hydrochloric acid.

Neutralization can be accomplished by techniques well known in the art,and before or after polymerization of the monomers comprising the hairstyling polymer.

d) Hair Conditioning Polymers

The compositions of the invention may include a hair conditioningpolymer for purposes of improved wet combing, dry combing and/orimproved manageability (e.g., frizz or static control). Hairconditioning polymers are typically used at a level of from about 0.001%to about 6% of the composition, more preferably from about 0.01% toabout 4% of the composition.

Cationic and zwitterionic hair conditioning polymers are preferred.Suitable hair conditioning polymers include cationic polymers having aweight average molecular weight of from about 5,000 to about 10 million,and will generally have cationic nitrogen-containing moieties such asquaternary ammonium or cationic amino moieties, and mixtures thereof.Cationic charge density should be at least about 0.1 meq/gram,preferably less than about 3.0 meq/gram, which can be determinedaccording to the well known Kjeldahl Method. Those skilled in the artwill recognize that the charge density of amino-containing polymers canvary depending upon pH and the isoelectric point of the amino groups.The charge density should be within the above limits at the pH ofintended use. Any anionic counterions can be utilized for the cationicpolymers so long as they are compatible.

The cationic nitrogen-containing moiety will be present generally as asubstituent, on a fraction of the total monomer units of the cationichair conditioning polymers. Thus, the cationic polymer can comprisecopolymers, terpolymers, etc. of quaternary ammonium or cationicamine-substituted monomer units and other non-cationic units referred toherein as spacer monomer units. Such polymers are known in the art, anda variety can be found in International Cosmetic Ingredient Dictionary,Sixth Edition, 1995, which is incorporated by reference herein in itsentirety.

Suitable cationic polymers include, for example, copolymers of vinylmonomers having cationic amine or quaternary ammonium functionalitieswith water soluble spacer monomers such as acrylamide, methacrylamide,alkyl and dialkyl acrylamides, alkyl and dialkyl methacrylamides, alkylacrylate, alkyl methacrylate, vinyl caprolactone, and vinyl pyrrolidone.The alkyl and dialkyl substituted monomers preferably have C₁ -C₇ alkylgroups, more preferably C₁ -C₃ alkyl groups. Other suitable spacermonomers include vinyl esters, vinyl alcohol (made by hydrolysis ofpoly-vinyl acetate), maleic anhydride, propylene glycol, and ethyleneglycol. The cationic polymers are described in detail in U.S. Pat. No.4,733,677 which is hereby incorporated by reference to further describethe cationic polymers used for conditioning purposes.

The cationic amines can be primary, secondary, or tertiary amines,depending upon the particular species and the pH of the composition. Ingeneral, secondary and tertiary amines, especially tertiary amines, arepreferred. The cationic polymers can comprise mixtures of monomer unitsderived from amine- and/or quaternary ammonium-substituted monomerand/or compatible spacer monomers.

Other cationic polymers that can be used include polysaccharidepolymers, such as cationic cellulose derivatives, cationic starchderivative, and cationic guar gum derivatives. Other materials includequaternary nitrogen-containing cellulose ethers as described in U.S.Pat. No. 3,962,418, and copolymers of etherified cellulose and starch asdescribed in U.S. Pat. No. 3,958,581, which descriptions areincorporated herein by reference.

e) Propellants

When the hair styling compositions are to be dispensed from apressurized aerosol container (e.g., certain hair sprays and mousses), apropellant which consists of one or more of the conventionally-knownaerosol propellants can be used to propel the compositions. A suitablepropellant for use can be generally any gas conventionally used foraerosol containers, preferably a liquifiable gas. Suitable propellantsfor use are volatile hydrocarbon propellants which can include liquifiedlower hydrocarbons of 3 to 4 carbon atoms such as propane, butane andisobutane. Other suitable propellants are hydrofluorocarbons such as1,2-difluoroethane (Hydrofluorocarbon 152A) supplied as Dymel 152A byDuPont. Other examples of propellants are dimethylether, nitrogen,carbon dioxide, nitrous oxide, and atmospheric gas. For hair sprays andmousses, the selection of appropriate hydrocarbons is made to provide astable system giving the desired spray/foam quality.

The aerosol propellant may be mixed with the present hair stylingcompositions and the amount of propellant to be mixed is governed bynormal factors well known in the aerosol art. Generally, for liquifiablepropellants, the level of propellant is from about 1% to about 60% byweight of the total composition. For hair sprays, the propellant levelis from about 10% to about 60% by weight of the total composition,preferably from about 15% to about 50% by weight of the totalcomposition. For mousses, the level of propellant is generally fromabout 1% to about 30% and more preferably from about 4% to about 15% byweight of the total composition.

Alternatively, pressurized aerosol dispensers can be used where thepropellant is separated from contact with the hair styling compositionsuch as a two compartment can of the type sold under the tradename SEPROfrom American National Can Corp.

Other suitable aerosol dispensers are those characterized by thepropellant being compressed air which can be filled into the dispenserby means of a pump or equivalent device prior to use. Such dispensersare described in U.S. Pat. No. 4,077,441, Mar. 7, 1978, Olofsson andU.S. Pat. No. 4,850,577, Jul. 25, 1989, TerStege, both incorporated byreference herein, and in U.S. Ser. No. 07/839,648, Gosselin et al.,filed Feb. 21, 1992, also incorporated by reference herein. Compressedair aerosol containers suitable for use are also those previouslymarketed by The Procter & Gamble Company under their tradename VIDALSASSOON AIRSPRAY® hair sprays.

Furthermore, non-aerosol foams may also be mixed with the present hairstyling composition such that the final composition is dispensable as astable foam. A composition is "dispensable as a stable foam" when itproduces a foam when dispensed from a package or container which iseither pressurized or equipped with an air or gas mixing device like theF2 non-aerosol foamer described in U.S. Pat. Nos. 5,271,530; 5,337,929;and 5,443,569; all of which are herein incorporated by reference.

f) Organopolysiloxane Microemulsions

The compositions of the present invention may contain anorganopolysiloxane microemulsion comprising polysiloxane particlesdispersed in a suitable carrier (typically aqueous) with the aid of asurfactant. The microemulsions are preferably included in an amount suchthat the composition contains from about 0.01% to about 10% of thedispersed polysiloxane, more preferably about 0.05% to about 6%, mostpreferably about 0.1% to about 4%. Typically, the composition willinclude about 0.02 to about 50% of the microemulsion.

Organopolysiloxane microemulsions can be produced by the emulsionpolymerization of organosiloxane having a low degree of polymerizationin a solvent comprising water. The organopolysiloxane is stabilized inthe microemulsion by a surfactant, preferably a nonionic surfactant andan ionic surfactant. The average particle size of the emulsion afteremulsion polymerization (corresponding to the organopolysiloxane in theemulsion) is preferably less than about 150 nanometers (nm), morepreferably less than about 100 nm, more preferably less than about 80nm, even more preferably less than about 60 nm, most preferably lessthan about 40 nm. When the average emulsion particle size exceeds 150nm, the stability of the blend with the other components of the haircare composition declines, and the external appearance of thecomposition will be negatively affected. Furthermore, the degree ofpolymerization (DP) of the polysiloxane after emulsion polymerization ispreferably in the range of from 3 to 5,000, more preferably in the rangeof from 10 to 3,000.

The organopolysiloxane in the microemulsion can be a linear or branchedchain siloxane fluid having a viscosity of about 20-3,000,000 mm² /s(cs), preferably 300-300,000 cs, more preferably 350-200,000 cs, at 25°C.

Suitable organopolysiloxanes preferably contain the difunctionalrepeating "D" unit: ##STR9## wherein n is greater than 1 and R¹ and R²are each independently C₁ -C₇ alkyl or phenyl. A mixture of siloxanesmay be used. Exemplary siloxanes include polydimethylsiloxane,polydiethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane,and polydiphenylsiloxane. Siloxane polymers with dimethylsiloxane "D"units are preferred from an economic standpoint. However, R¹ and R² mayindependently be a functional group other than methyl, e.g., aminoalkyl,carboxyalkyl, haloalkyl, acrylate, acryloxy, acrylamide, mercaptoalkylor vinyl. However, preferred organopolysiloxanes are those which do notcontain amino groups in combination with hydroxyl groups.

The siloxane may be terminated with hydroxy groups, alkoxy groups suchas methoxy, ethoxy, and propoxy, or trimethylsiloxy groups, preferablyhydroxy or trimethylsiloxy.

The emulsion can be prepared by the emulsion polymerization processdescribed in EP 459500 (published Dec. 4, 1992), incorporated herein byreference. In that process, stable, oil free polysiloxane emulsions andmicroemulsions are prepared by mixing a cyclic siloxane, a nonionicsurfactant, an ionic surfactant, water, and a condensationpolymerization catalyst. The mixture is heated and agitated atpolymerization reaction temperature until essentially all of the cyclicsiloxane is reacted, and a stable, oil free emulsion or microemulsion isformed. The reaction mix, especially surfactant levels, and conditionsare controlled in order to provide the desired organopolysiloxaneparticle size. The emulsions and microemulsions typically have a pH ofabout 3 to about 10 (e.g., 6-7.5), and contain about 10% to about 70% byweight siloxane polymer, preferably about 25% to about 60%, about 0% toabout 30% by weight nonionic surfactant, about 0% to about 30% by weightionic surfactant, preferably about 0% to about 20%, the balance beingwater. Preferred emulsions and methods of making them are furtherdescribed in U.S. patent application Ser. No. 08/929,721, filed on Sep.15, 1997 in the names of Ronald P. Gee and Judith M. Vincent,incorporated herein by reference in its entirety.

Microemulsions can also be produced by the emulsion polymerizationprocess described in EPA 0268982, published Jun. 6, 1988, assigned toToray, incorporated herein by reference in its entirety. In thisprocess, the microemulsion is prepared by a process in which a crudeemulsion, consisting of polysiloxane having a low degree ofpolymerization, a first surfactant (anionic, cationic, and nonionicsurfactants), and water, is slowly dripped into an aqueous solutioncontaining a catalytic quantity of a polymerization catalyst and asecond surfactant which acts as an emulsifying agent (which may be thesame as the first surfactant, however, the surfactants should becompatible in the reaction mixture considering the ionicity of thereaction mixture). The reaction mix and conditions are controlled toprovide the desired organopolysiloxane particle size. Therefore, adropwise addition of the crude emulsion into the aqueous solution ofcatalyst and surfactant of 30 minutes or longer is preferred in order toproduce microemulsions having smaller particle sizes. In addition, thequantity of surfactant used in the catalyst plus the surfactant aqueoussolution is from about 5 to about 70 weight %, more preferably fromabout 25 to about 60 per 100 weight parts polysiloxane in the crudeemulsion.

Any conventional nonionic surfactant can be used to prepare themicroemulsion. Exemplary types of nonionic surfactants include siliconepolyethers, both grafted and linear block, ethoxylated fatty alcohols,ethoxylated alcohols, ethoxylated alkyl phenols, Isolaureth-6(polyethylene glycol ether of branched chain aliphatic C₁₂ containingalcohols having the formula C₁₂ H₂₅ (OCH₂ CH₂)₆ OH), fatty acidalkanolamides, amine oxides, sorbitan derivatives (e.g., commerciallyavailable from ICI Americas, Inc., Wilmington, Del., under thetradenames SPAN and TWEEN), and propylene oxide-ethylene oxide blockpolymers (e.g., commercially available from BASF Corp., Parsippany, N.J.under the trademark PLURONIC). Ionic surfactants useful in preparing themicroemulsion include any conventional anionic surfactant such assulfonic acids and their salt derivatives. Ionic surfactants alsoinclude any conventional cationic surfactant used in emulsionpolymerization. Surfactants of these types are commercially availablefrom a number of sources. Specific examples of these surfactant typesare also disclosed in the above referenced patent application Ser. No.08/929,721.

The surfactant can be used in the form of a single type of surfactant(e.g., anionic, cationic or nonionic), or the surfactant can be used asa combination of two or more types provided that the mixture iscompatible. Preferred combinations of surfactant types include thecombination of two or more types of anionic surfactants, the combinationof two or more types of nonionic surfactants, the combination of two ormore types of cationic surfactants, the combination of two or more typesof surfactants selected from both the anionic and nonionic surfactants;and the combination of two or more types of surfactants selected fromboth the cationic and nonionic surfactants.

The catalyst employed in the emulsion polymerization may be any catalystcapable of polymerizing cyclic siloxanes in the presence of water,including condensation polymerization catalysts capable of cleavingsiloxane bonds. Exemplary catalysts include strong acids and strongbases, ionic surfactants such as dodecylbenzenesulfonic acid, phasetransfer catalysts, and ion exchange resins where a catalyst is formedin situ. As will be understood by those skilled in the art, a givensurfactant may also serve as the polymerization catalyst (e.g.,alkylbenzenesulfonic acids, or quaternary ammonium hydroxides or saltthereof may function as both a surfactant and the polymerizationcatalyst).

A surfactant system, catalyst and resulting microemulsion suitable foruse in the compositions of the present invention can be selected by theskilled artisan considering the ionicity of the composition. In general,these materials are selected such that the total composition will becompatible.

Organopolysiloxane microemulsions are available from a number ofcommercial sources. The following organopolysiloxanes are manufacturedby Dow Corning of Midland, Mich.:

    ______________________________________                                        Microemulsions containing dimethicone copolyol:                               Micro-              Internal                                                  emulsion            phase              Si                                     Trade               viscosity          particle.                              Name   Si Type      (cps)    Surfactant                                                                              size, nm                               ______________________________________                                        DC     Dimethylsiloxanol,                                                                         70-90M   Triethanolamine                                                                         <50                                    2-5791 Dimethyl              dodecylbenzene                                          cyclosiloxane         sulfonate,                                                                    Polyethylene                                                                  oxide                                                                         lauryl ether                                     DC     Dimethylsiloxanol,                                                                         70-90M   Triethanolamine                                                                         <40                                    2-5791 -                                                                             Dimethyl              dodecylbenzene                                   sp     cyclosiloxane         sulfonate,                                                                    Polyethylene                                                                  oxide                                                                         lauryl ether                                     DC     Dimethylsiloxanol,                                                                         1-2M     Cetrimonium                                                                             <30                                    2-5932 Dimethyl              Chloride,                                               cyclosiloxane         Trideceth-12                                     ______________________________________                                    

    ______________________________________                                        Microemulsions not containing dimethicone copolyol:                           Microe-            Internal                                                   mulsion            phase               Si                                     Trade              viscosity           particle.                              Name  Si Type      (cps)    Surfactant size, nm                               ______________________________________                                        DC 2- Dimethylsiloxanol,                                                                         15-20M   Triethanolamine                                                                          124                                    1470 -                                                                              Dimethyl              dodecylbenzene                                    LP    cyclosiloxane         sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                      DC 2- Dimethylsiloxanol,                                                                         4-8M     Triethanolamine                                                                          94                                     1470 -                                                                              Dimethyl              dodecylbenzene                                    MP    cyclosiloxane         sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                      DC 2- Dimethylsiloxanol                                                                          10-30M   Cetrimonium                                                                              50-80                                  1716  with methyl           Chloride, Trideceth-                              MEM   silsequioxane,        12                                                      Octamethyl                                                                    cyclotretrasiloxane                                                     DC 2- Mercapto-    --       Cetrimonium                                                                              50-70                                  8937  siloxane              Chloride, Trideceth-                                                          12                                                DC 2- Dimethylsiloxanol,                                                                         15-20M   Triethanolamine                                                                          <50                                    1470  Dimethyl              dodecylbenzene                                          cyclosiloxane         sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                      DC 2- Dimethylsiloxanol,                                                                         4-8M     Triethanolamine                                                                          <40                                    1845  Dimethyl              dodecylbenzene                                          cyclosiloxane         sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                      DC 2- Dimethylsiloxanol,                                                                         60-70M   Triethanolamine                                                                          <35                                    1845 -                                                                              Dimethyl              dodecylbenzene                                    HV    cyclosiloxane         sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                      DC 2- Dimethylsiloxanol,                                                                         100-600M Triethanolamine                                                                          ≦50                             1550  Dimethyl              dodecylbenzene                                          cyclosiloxane         sulfonate,                                                                    Polyethylene oxide                                                            lauryl ether                                      DC 2- Dimethylsiloxanol,                                                                         1-2M     Cetrimonium                                                                              <30                                    1281  Dimethyl              Chloride, Trideceth-                                    cyclosiloxane         12                                                DC 2- Dimethyl,    4-6M     Cetrimonium                                                                              ≦30                             8194  aminomethyl propyl    Chloride, Trideceth-                                    siloxane              12                                                ______________________________________                                    

Where the hair styling polymer is an anionic acrylate polymer, DC2-1845, and DC 2-5791 are preferred microemulsions. When the hairstyling polymer is a cationic polymer comprising nitrogen, theDC-2-8194, DC 2-1281, and DC 2-5932 are preferred.

g) Silicone Polyether Surfactant

Compositions of the present invention may contain a silicone polyethersuitable for stabilizing the organopolysiloxane microemulsion. Siliconepolyethers are preferably included where the composition contains about40% or more of a C₁ -C₃ monohydric alcohol.

The silicone polyether comprises a polymeric portion comprisingrepeating organosiloxane units, and a polymeric portion comprisingrepeating alkylene oxide units (i.e., a silicone-polyoxyalkylenecopolymer). Suitable silicone polyethers are those which are surfaceactive in the carrier employed in the compositions of the invention. Aswill be understood in the art, the surface activity of the siliconepolyether will depend on the molecular weight of the polymeric portioncomprising repeating organosiloxane units. This portion should be ofsufficiently large molecular weight such that it is insoluble in thecarrier, yet not so large that it renders the whole molecule insolublein the carrier. The silicone polyether is preferably used in an amountof from about 0.02% to about 7%, more preferably about 0.05% to about5%, of the total composition.

The silicone polyether may be a silicone--linear polyoxyalkylene blockcopolymer (wherein the polymeric backbone comprises silicone blocks andpolyoxyalkylene blocks, optionally having grafts), a silicone--graftpolyoxyalkylene copolymer (wherein the polymeric backbone comprisessilicone blocks and the polyoxyalkylene blocks are present as graftsrather than in the backbone), or a mixture thereof Linearpolyoxyalkylene block copolymers are preferred.

Preferred silicone linear block polyethers suitable for use herein havethe formula (I):

    M'D.sub.b D'.sub.c M'

wherein

M' is a monofunctional unit R₂ R'SiO_(1/2) ;

D is a difunctional unit R₂ SiO_(2/2) ;

D' is a difunctional unit RR'SiO_(2/2) ;

R is independently H, C₁ -C₆ alkyl, or aryl, preferably H or C₁ -C₄alkyl, more preferably CH₃ ;

R' is independently, an oxyalkylene containing moiety, H, or CH₃ ;

b is an integer of from about 10 to about 1000, preferably about 10 toabout 500, more preferably about 20 to about 90; and

c is an integer of from 0 to about 100, preferably 0 to about 50, morepreferably c is 0, provided that when c is 0, at least one M contains anoxyalkylene moiety.

Preferred R' in structure (I) are those having the formula:

    --R"(OC.sub.n CH.sub.2n).sub.y --R'"

wherein

R" is a divalent radical for connecting the oxyalkylene portion ofmoiety R' to the siloxane backbone, preferably --(C_(m) H_(2m))--,wherein m is an integer of from 2 to 8, preferably from 2-6, morepreferably from 3-6;

R'" is a terminating radical for the oxyalkylene portion of the moietyR', e.g.,

H, hydroxyl, C₁ -C₆ alkyl, aryl, alkoxy (e.g., C₁ -C₆) or acyloxy (e.g.,C₁ -C₆), preferably hydroxyl;

n is an integer of from 2 to 4, preferably 2 to 3 (i.e., the oxyalkylenegroup may contain ethylene oxide, propylene oxide and/or butylene oxideunits); and

y is an integer of 1 or greater, wherein the total y from alloxyalkylene units in the copolymer is 10 or greater.

The oxyalkylene moiety R' may be a random copolymer, a block copolymeror a mixture thereof Preferred R' groups in structure (I) are thosewherein the oxyalkylene units are selected from ethylene oxide units(EO), propylene oxide units (PO), and mixtures thereof More preferredare those wherein the oxyalkylene units have an ethylene oxide unit (EO)to propylene oxide unit (PO) ratio of EO₁₀₋₁₀₀ PO₀₋₁₀₀, more preferablyEO₂₀₋₇₀ PO₂₀₋₇₀, most preferably EO₃₀₋₇₀ PO₃₀₋₇₀, based on the totaloxyalkylene in the silicone polyether.

Particularly preferred silicone polyethers at relatively high VOCs(e.g., greater than 40%) are those having the formula: ##STR10## whereinn is as defined above, and x is independently an integer of 1 orgreater, a and b independently are an integer of from about 15 to about30, and w is from about 20 to about 200, more preferably from about 30to about 200. Such silicone polyethers are commercially available fromGoldschmidt Chemical Company under the tradename TEGOPREN 5830.

Preferred silicone graft polyethers for use herein are those having theformula (II):

    MD.sub.b D'.sub.c M

wherein:

M is a monofunctional unit R₃ SiO_(1/2),

D is a difunctional unit R₂ SiO_(2/2),

D' is a difunctional unit RR'SiO_(2/2),

R is independently H, C₁ -C₆ alkyl, or aryl, preferably H or C₁ -C₄alkyl, more referably CH₃,

R' is an oxyalkylene containing moiety,

b is an integer of from about 10 to about 1000, preferably about 100 toabout 500

c is an integer of from 1 to about 100, preferably 1 to about 50.

Preferred R' are those having the formula

    --R"(OC.sub.n CH.sub.2n).sub.y --R'"

wherein

R" is a divalent radical for connecting the oxyalkylene portion ofmoiety R' to the siloxane backbone, preferably --(C_(m) H_(2m))--,wherein m is an integer of from 2 to 8, preferably 2-6, more preferably3-6;

R'" is a terminating radical for the oxyalkylene portion of moiety R',e.g., H, hydroxyl, C₁ -C₆ alkyl, aryl, alkoxy (e.g., C₁ -C₆) or acyloxy(e.g., C₁ -C₆), preferably hydroxy or acyloxy, more preferably hydroxyl;

n is an integer of from 2 to 4, preferably 2 to 3 (i.e., the oxyalkylenegroup may contain ethylene oxide, propylene oxide and/or butylene oxideunits); and

y is 1 or greater.

The oxyalkylene moiety R' may be a random copolymer, a block copolymeror a mixture thereof Preferred R' groups are those wherein theoxyalkylene units are selected from ethylene oxide units (EO), propyleneoxide units (PO), and mixtures thereof More preferred are those whereinthe oxyalkylene units have an ethylene oxide unit (EO) to propyleneoxide unit (PO) ratio of EO₁₀₋₁₀₀ PO₀₋₁₀₀, more preferably EO₁₀₋₃₀PO₁₋₃₀, based on the total oxyalkylene in the silicone polyether.

In this regard, Table 1 shows some representative silicone graftpolyethers:

                  TABLE 1                                                         ______________________________________                                        Silicone                                                                      Polyether*                                                                            Structure Weight % EO                                                                              Weight % PO                                                                            HLB**                                   ______________________________________                                        A       EO        19         0        6.8                                     B       EO        40         0        8.0                                     C       EO/PO     34         0.4      6.8                                     D       EO/PO     41         12       8.2                                     E       EO/PO     34         39       5.0                                     F       EO/PO     32         42       6.4                                     G       EO/PO     30         40       5.7                                     ______________________________________                                         *Silicone Polyethers A and B contain less than 20 D units and less than 5     D' units. Silicone Polyethers C-G contain from 100-200 D units and 10-30      D' units.                                                                     **Hydrophilic lipophilic balance (HLB) is determined by calculating the       weight percent of EO and dividing this value by five.                    

Silicone polyethers of this type are further described in the abovereferenced patent application Ser. No. 08/929,721.

Siloxane-oxyalkylene copolymers, i.e., silicone polyethers, can beprepared according to methods generally described in the standard texton silicone chemistry entitled "Chemistry and Technology of Silicones,"by Walter Noll, Academic Press Inc., Orlando, Fla., (1968), on pages373-376. Silicone polyethers are also available from a number ofcommercial sources such as:

    ______________________________________                                                            Silicone          Molecular                               Trade Name                                                                             Supplier   Content %                                                                              EO and/or PO                                                                           Weight                                  ______________________________________                                        D.C.Q2-5220                                                                            Dow Corning.sup.1                                                                        14       EO & PO  3102                                    D.C.193  "          33       EO       --                                      D.C.190  "          24       EO & PO  2570                                    D.C.Q4-3667                                                                            "          37       EO       2400                                    Silwet L-7200                                                                          OSI.sup.2  31       EO & PO  19,000                                  Tegopren 5830/                                                                         Goldschmidt                                                                              55       40% EO/60%                                                                             7800                                    Abil 8830                                                                              A.G..sup.3          PO                                               Tego 5830 - A                                                                          "          50       30% E0/70%                                                                             9000                                             "                   PO                                               Tego 5830 - B                                                                          "          50       60% EO/40%                                                                             9000                                             "                   PO                                               Abil B8851                                                                             "          --       EO & PO  >1400                                   Abil B8863                                                                             "          --       EO & PO  >3000                                   Abil EM 97                                                                             "          75       60% EO/40%                                                                             14,000-                                 neat                         PO       15,000                                  ______________________________________                                         .sup.1 Dow Corning of Midland, Michigan                                       .sup.2 OSI Specialties of Lisle, IL.                                          .sup.3 Hopewell, VA                                                      

Other silicone polyethers are available as SF-1188 offered by GeneralElectric of Waterford, N.Y., and KF353A offered by Shin Etsu Siliconesof America of Torrance, Calif. Additional silicone polyethers aredescribed in U.S. Pat. No. 4,871,529, incorporated herein by reference.

h) Other Optional Components

Compositions of the invention may contain a variety of other ingredientssuch as are conventionally used in a given product form. Thecompositions hereof may be in the form of a hairspray, mousse, gel,lotion, cream, pomade, spray-on product such as spray-on gel, heatprotectant spray, volumizing spray, spritz, hair tonic, and the like.The compositions may be aerosol or non-aerosol. Such compositions aredescribed, for example in California Code of Regulations, Regulation forReducing Volatile Organic Compound Emissions from Consumer Products,Amendment 2, Consumer Products, Sections 94507-94717, Title 17, filedSep. 19, 1991 and effective Oct. 21, 1991; and Jellinek, J. S.,Formulation and Function of Cosmetics, Wiley-Interscience, 1970; bothincorporated herein by reference.

Preferred Compositions of the Present Invention

Particularly preferred compositions of the invention comprise, inaddition to the hair styling polymer and carrier, the followingcomponents in the above described amounts: from about 0.1% to about 15%,of the hair styling polymer, more preferably a silicone-grafted polymer;0.01% to about 6%, more preferably about 0.01% to about 4%, of anorganopolysiloxane microemulsion; from about 5% to about 99%, of water;and a plasticizer in the above described amounts.

Method of Making

The hair styling compositions of the present invention can be made usingconventional formulation and mixing techniques. The hair styling polymerand the solvent are mixed to provide a homogeneous mixture. Any otheringredients are then added and mixed to yield the final composition. Ifthe polymer is neutralized, the neutralizer is preferably added prior toaddition of other ingredients. For hair spray products, the compositionis packaged in conventional mechanical pump spray devices, oralternatively, in the case of aerosol sprays products, the compositionis packaged in conventional aerosol canisters along with an appropriatepropellant system (also applicable for mousses). Other hair stylingcompositions including tonics, lotions, and gels, are typically packagedin a conventional bottle or tube.

High water products, containing less than about 50% VOC, such as mousse(e.g., 16% VOC or less) and gel (e.g., 6% VOC or less), and containingsilicone grafted hair styling copolymer derived from monomers containingacid functional groups are preferably prepared in the following manner.The silicone grafted polymer is dissolved in the compatible, organicsolvent, e.g., ethanol or isopropanol, prior to neutralization of thepolymer. The solvent used to dissolve the polymer should not containsignificant amounts of water and is preferably essentially free ofwater. If water is added prematurely, either before neutralization orbefore less than 10% neutralization of the polymer (e.g., neutralizationof less than 50% of the acid groups where acid groups are 20% of thepolymer structure), the polymer tends to precipitate as a whiteinsoluble mass. Attempts to complete neutralization after precipitationare generally unsuccessful.

Where water is added after neutralization has occurred, the film qualityproduced from these modified polymers tends to have a desirable slickand lubricious surface (without intending to be bound by theory, this isusually indicative of silicone present at the surface). Preferredcompositions are clear to translucent in appearance. The composition isalso stable, preferably retaining within about 10% of its initialclarity with no noticeable precipitate formation for a period of about 6months or more.

Completion of the neutralization reaction is important for good productclarity, good shampoo removability, and good stability of thecomposition. However, in compositions having low solvent levels and aneffective level of polymer (1-5%), e.g., in typical mousse and gelformulas, the viscosity of the system can increase dramatically withneutralization. This viscosity increase can hinder completion of theneutralization reaction. Therefore, steps should be taken to ensure thatthe neutralization reaction is complete. For example, this can beensured by one or more of the following techniques:

1. When the viscosity of the system becomes very thick (typically whenabout 10% of the polymer has been neutralized), a portion of the water(preferably a minimum 27% of the batch in 6% VOC systems and minimum 10%of the batch in 16% VOC systems) can be added to the system. The wateris used in an amount sufficient to lower the viscosity enough in orderto achieve good mixing. It is preferred from the standpoint ofmanufacturing efficiency to add the water portion in one step. However,the water may be added in small increments (e.g., 5% of the batchwater), between incremental additions of neutralizer. For example, afterthe first neutralizer addition (sufficient to neutralize up to about 10%of the polymer) is added with vigorous agitation, then 5% of the batchwater can be added, then enough neutralizer to neutralize another 2-4%of the polymer can be added, then another 5% of the batch water additioncan be made. This process continues until all the neutralizer is addedto the batch. Application of high shear rates to the system, such as canbe generated by a Teckmar type milling device, may also be utilized toincrease the mass transfer rate, thereby resulting in faster reactioncompleteness.

2. When a high viscosity has been reached a specially designed highviscosity mixing device, e.g., a dough mixer, may be used. The system ismixed for many hours until reaction completeness can verifiedanalytically (titration, FTIR, or pH), typically up to about 12 hours. Anitrogen blanketed, enclosed system or the like is preferably used tominimize solvent loss during the mix time.

3. Use specialized pressure vessel equipment, heat and agitation. Heatis to be applied while avoiding evaporation of the solvent. Therefore, anitrogen blanketed pressure vessel should be employed.

The first and third methods above are preferred as being the mostefficient. In the absence of the availability of heated pressure vessels(i.e. ambient conditions), the first method is preferred.

In addition, where the composition contains hydrophobic, oily componentssuch as perfume or isoparaffins, steps must be taken to ensure goodemulsification of the hydrophobic component in the composition. However,emulsion compositions containing alcohols can be difficult to formulate.Some hydrophobic components such as those mentioned above are relativelydifficult to emulsify, typically requiring very high levels ofsurfactants in order to create reasonably clear systems (which aretypically microemulsions). These high levels of surfactants can overplasticize the silicone-grafted polymer, making it unacceptably sticky.

It has been found in the present invention that the hydrophobiccomponents can be readily emulsified by the use of a combination oforganic and inorganic neutralizers. Without intending to be limited bytheory, it is believed that this combination of neutralizers help thepolymer itself to function as an emulsifier by imparting surfactant-likequalities to the polymer (i.e., a portion of the polymer is relativelyhydrophobic and a portion of the polymer is relatively hydrophilic).

The neutralization system comprises a fatty amine neutralizer(preferably selected from dimethyl lauryl amine, dimethyl myristylamine, amine methyl propanol, dimethylstearyl amine, TEA, and mixturesthereof, more preferably dimethyl lauryl amine, dimethyl myristyl amineand mixtures thereof), in combination with an inorganic neutralizer(preferably metal hydroxides, more preferably NaOH and/or KOH, mostpreferably NaOH). The amine neutralized acid groups tend to be morehydrophobic than the inorganic neutralized acid groups. Withoutintending to be bound by theory, it is believed that the amine groupsemulsify the hydrophobic components and the inorganic groups providesufficient water solubility/compatibility and shampoo removability.

When such dual neutralizers are employed, the order of componentaddition and other process variables become important for preparing theclearest, most stable product. The preferred order of addition andprocess is as follows: With vigorous agitation:

1. Completely dissolve the polymer in a compatible solvent systemcontaining the water soluble, organic solvent (e.g., ethanol orisopropanol).

2. Add the fatty amine neutralizer in a weight ratio of from 1-6 amineto hydrophobic components to 1-2 amine to hydrophobic components.

3. Add the hydrophobic components.

4. Add any plasticizers.

5. Add the inorganic neutralizer at a level that represents 10%-20% ofthe polymer (or 50-100% of the available acid groups in a polymer with20% acrylic acid).

6. When the system becomes very thick (similar to peanut butter), mixthe system for at least 10 minutes. Then add water to the mixture in themanner described above, preferably as described for the preferredembodiment of the first method.

7. Mill the system with a high shear mixer such as made by Teckmar forat least 10 minutes.

8. Add the balance of the water and other ingredients required to makethe final composition. Gels are preferably dearated, more preferablybefore the addition of any thickeners.

Whether the hair styling polymer is a silicone graft polymer or otherpolymer, when the compositions of the present invention comprise asilicone microemulsion, it is important to add the siliconemicroemulsions to the system when some water (or other polar material)is present. The water helps to maintain the stability of the siliconemicroemulsions in the composition. The amount of water which ispreferably present depends on the type of hair styling polymer and thepresence and type of silicone copolyol. If the composition does notcontain a silicone copolyol, at least about 15% water is preferablypresent when the polymer comprises a silicone graft polymer and at leastabout 30% water when the polymer is other than a silicone graft polymer.When the composition contains other dimethicone copolyols and thepolymer comprises a silicone graft polymer, at least about 10% water ispreferably present. Where the polymer is other than a silicone graftpolymer, at least about 25% water is present.

Additionally, it is desirable to not impart high shear rates to thecomposition once the silicone microemulsion has been added, since shearmight break the emulsion. Also, the silicone microemulsion is typicallyadded after any thickeners or surfactants.

Method of Use

The compositions of the present invention are used in conventional waysto provide the hair care benefits of the present invention. Such methodsgenerally involve application of an effective amount of the product toslightly damp or wet hair before after the hair is dried and arranged toa desired style. Application of the product is normally effected byspraying or atomizing the product using an appropriate device, e.g. amechanical pump spray, a pressurized aerosol container, or otherappropriate means. Other hair styling compositions including tonics,lotions, and gels, are typically dispensed from a conventional bottle ortube, and applied directly to the hair or first dispensed to the handand then to the hair. The composition is then dried or allowed to dry.By "effective amount" is meant an amount sufficient to provide the hairhold and style benefits desired. In general, from about 0.5 g to about30 g of product is applied to the hair, depending upon the particularproduct formulation, dispenser type, length of hair, and type of hairstyle.

EXAMPLE

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.Ingredients are identified by chemical or CTFA name.

Examples I-III

The following are mousse compositions representative of the presentinvention:

    ______________________________________                                        Concentrate composition:                                                                         I     II      III                                          ______________________________________                                        Ethanol (200 proof)  14.00   14.00   10.00                                    Acrylate Dimethicone Copolymer.sup.1                                                               4.00    3.50    3.0                                      Dimethyl Laurylamine.sup.2                                                                         0.40    0.16    --                                       Dimethyl Stearylamine.sup.3                                                                        --      --      0.30                                     Isododecane.sup.4    0.50    0.50    0.50                                     Perfume              0.10    0.10    0.10                                     Sodium Hydroxide Solution (30% active)                                                             1.10    1.07    0.88                                     Water                73.94   74.81   79.66                                    Polyquaternium 47 (20% active).sup.5                                                               2.50    2.50    2.50                                     Lauramide DEA.sup.6  0.20    0.20    0.20                                     Steareth 21.sup.7    0.10    0.10    0.10                                     Steareth 2.sup.8     0.15    0.15    0.10                                     Silicone Microemulsion (25% active).sup.9                                                          2.00    2.00    1.75                                     Preservatives        0.91    0.91    0.91                                     ______________________________________                                         .sup.1 60/20/20 Tetrbutylacrylate/Acrylic Acid/12K silicone macromer,         polymer molecular weight 128,000, e.g., Diahold ME, Mitsubishi Chemical       Corp.                                                                         .sup.2 C12 Alkyl Dimethyl Amine, AT1295 LT                                    .sup.3 C14 Alkyl Dimethyl Amine, AT1495 LT                                    .sup.4 Permethyl 99A, Presperse Inc.                                          .sup.5 Merquat 2001, Calgon                                                   .sup.6 Monamide 716, Mona                                                     .sup.7 BRU 721, ICI                                                           .sup.8 BRU 72, ICI                                                            .sup.9 DC2-5791- Silicone microemulsion from Dow Corning with a particle      size of 37 nm, an anionic/nonionic surfactant system, and a PDMS silicone     with an internal phase viscosity = 95,000 cps.                           

A first premix is prepared as follows. Completely dissolve the AcrylateDimethicone Copolymer in ethanol with vigorous agitation. Add theDimethyl Laurylamine or the Dimethyl Myristalamine, Isododecane andperfume. With vigorous agitation, slowly add the NaOH and mix to achievea complete neutralization reaction. Next, add half of the water and milluntil a uniform, relatively thin mixture results.

Separately, a second premix is prepared as follows. First, dissolve thesurfactants (Lauramide DEA, Steareth 721, & Steareth 21) in theremaining water with heat (120° F.) and agitation. Next, remove thepremix from heat when surfactants are completely dissolved. Adjust thepH of the Polyquaternium-47 with NaOH to be equal to that of thecompleted first premix (about 7.5-8.0 pH). With vigorous agitation, addthe pH adjusted Polyquaternium 47, preservatives, and then the siliconemicroemulsion.

Proceed to combine Premix 1 and Premix 2 with vigorous agitation to forma concentrate. Combine the concentrate with suitable propellants andpackage in a conventional manner. For example, the final composition maycontain: Concentrate Composition (93 wt. %); Hydrofluorocarbon 152A(4.76 wt. %); and Isobutane A31 (2.24 wt. %).

Example IV

The following is a mousse composition representative of the presentinvention:

    ______________________________________                                        Concentrate composition:                                                      Component             Weight %                                                ______________________________________                                        Polyquaternium 11 (20% active).sup.1                                                                4.75                                                    Polyquaternium 4.sup.2                                                                              0.95                                                    Perfume               0.10                                                    Water                 89.49                                                   Glycerin              0.30                                                    Propylene glycol      0.20                                                    Lauramide DEA.sup.3   0.20                                                    Steareth 21.sup.4     0.10                                                    Silicone Microemulsion (25% active).sup.5                                                           3.00                                                    Preservatives         0.91                                                    ______________________________________                                         .sup.1 Gafquat  755N, ISP                                                     .sup.2 Celquat H100, National Starch                                          .sup.3 Monamide 716, Mona                                                     .sup.4 BRIJ 721, ICI                                                          .sup.5 DC2-5932 silicone microemulsion from Dow Corning with a particle       size of 24 nm, a cationic surfactant system, and a silicone with an           internal phase viscosity = 1,200 cps.                                    

The first premix is prepared by starting with 1/2 of the water (saveremaining 1/2 for premixing Silicone Microemulsion, preservatives andsurfactants). Next, add the Celquat H-100 and mix until uniformlydissolved in ethanol/water. Add the Gafquat-755N and mix until uniformlydissolved. With vigorous agitation, add the propylene glycol and theglycerin.

The second premix is prepared by dissolving the surfactants (LauramideDEA, Steareth 21) in the remaining water with heat (120° F.) andagitation. Remove the mix from heat when the surfactants are completelydissolved. Next, add the preservatives, the perfume, and the siliconemicroemulsion to the mix with vigorous agitation.

The final concentrate step involves combining the first and secondpremixes under vigorous agitation and placing the concentrate in asuitable aluminum can at 7% of total fill with an appropriate moussevalve. The valve is crimped to the can and a vacuum is applied todeaerate. The can is then pressurized with propellant.

    ______________________________________                                        Can Composition:     Weight %                                                 ______________________________________                                        Concentrate Composition (above)                                                                    93.00                                                    Hydrofluorocarbon 152A (propellant)                                                                4.76                                                     Isobutane (A31 propellant)                                                                         2.24                                                     ______________________________________                                    

Examples V and VI

The following is a gel composition representative of the presentinvention:

    ______________________________________                                        Component              Weight %                                               ______________________________________                                                               V       VI                                             Isopropanol            7.00    4.00                                           Acrylate Dimethicone Copolymer.sup.1                                                                 3.50    2.00                                           Dimethyl Myristalamine.sup.2                                                                         0.23    0.13                                           Isododecane.sup.3      0.50    0.50                                           Perfume                0.10    0.10                                           Diethylene Glycol.sup.4                                                                              0.35    0.35                                           Sodium Hydroxide Solution (30% active)                                                               1.04    0.56                                           Water                  82.87   87.20                                          Glycerol Polymethacrylate Mixture.sup.7                                                              --      0.25                                           Glycerine              0.25    --                                             Hydroxylpropyl Guar.sup.5                                                                            1.25    1.00                                           Silicone Microemulsion (25% active).sup.6                                                            2.00    3.00                                           Preservatives          0.91    0.91                                           ______________________________________                                         .sup.1 60/20/20 Terbutylacrylate/Acrylic Acid/12K silicone macromer,          polymer molecular weight 128,000                                              .sup.2 C14 Alkyl Dimethyl Amine, AT1495 LT                                    .sup.3 Permethyl 99A, Presperse Inc.                                          .sup.4 Diethylene glycol, Ashland                                             .sup.5 Jaguar HP105, RhonePoulenc                                             .sup.6 DC2-5791 (sp) silicone microemulsion from Dow Corning with a           particle size of 37 nm, an anionic/nonionic surfactant system, and a          silicone with an internal phase viscosity = 95,000.                           .sup.7 Lubrajel Oil, distributed by ISP, UnitedGuardian                  

A first premix is prepared by completely dissolving the AcrylateDimethicone Copolymer in ethanol with vigorous agitation. Undercontinuing agitation, add the Dimethyl Myristalamine, Isododecane andperfume, the Diethylene glycol, then slowly add the NaOH and mix toachieve a complete neutralization reaction. Next, add 33% of the batchwater (premixed with glycerin or Lubrajel oil, preservatives) and milluntil a uniform, relatively thin mixture results.

Separately, a second premix is prepared by dissolving the Hydroxylpropylguar in 43% of the batch water (100° F.) until the guar is fullyhydrated. Add the silicone microemulsion (premixed with the remainingwater) to the mix with mild agitation.

Combine Premix 1 and Premix 2 with vigorous agitation to form aconcentrate.

Example VII

The following is a gel composition representative of the presentinvention:

    ______________________________________                                        Component             Weight %                                                ______________________________________                                        PVP.sup.1             2.00                                                    PVP/VA Copolymer (50% active).sup.2                                                                 3.00                                                    Isosteareth 20.sup.3  0.30                                                    Perfume               0.20                                                    Polyquaterium-11 20% active.sup.4                                                                   2.00                                                    Water                 87.10                                                   Propylene Glycol      0.20                                                    Glycerin              0.25                                                    Hydroxylpropyl Guar.sup.5                                                                           1.00                                                    Silicone Microemulsion (25% active).sup.6                                                           3.00                                                    Preservatives         0.95                                                    ______________________________________                                         .sup.1 PVP K30, ISP                                                           .sup.2 Luviskol VA 73W, BASF                                                  .sup.3 Arosurf 66 E20, Witco                                                  .sup.4 Celquat H100, National Starch                                          .sup.5 Jaguar HP105, RhonePoulenc                                             .sup.6 DC 21281  Dow Corning silicone microemulsion with a cationic           surfactant system and with a particle size of 25nm and an internal phase      viscosity Of 1,200 cps. (no dimethicone copolyol)                        

The premix is prepared by completely dissolving the PVP and PVP/VA in30% of the batch water (120° F.) with vigorous agitation. Undercontinued agitation, add the Isosteareth-20 and the perfume, and thenremove the mix from the heat. While still vigorously agitating, add theGlycerin, the Polyquaternium-11, and the preservatives.

The final mix is prepared under vigorous agitation by dissolving theJaguar in 50% of the batch water (155° F.) until the Jaguar is fullyhydrated. With mild agitation, add premix and then the siliconemicroemulsion (premixed with the remaining water).

What is claimed is:
 1. A personal care composition suitable for stylinghair comprising:a) from about 0.01% to about 20%, by weight of thecomposition, of a hair styling polymer; and b) a carrier comprising:i)at least about 0.5% to about 99.9%, by weight of the composition, of afirst solvent selected from the group consisting of water; water solubleorganic solvents; organic solvents which are strongly to moderatelystrong in hydrogen bonding parameter; and mixtures thereof; wherein thefirst solvent is other than C1-C3 monohydric alcohol, C1-C3 ketone, andC1-C3 ether; and ii) from about 0.5% to about 55%, by weight of thecomposition, of a second solvent selected from the group consisting ofC1-C3 monohydric alcohols, C1-C3 ketones, C1-C3 ethers, and mixturesthereof; wherein the composition is characterized by having a StiffnessValue (SV) and a Curl Retention Index (CRI), wherein

    SV≦[(0.703×CRI)-0.425)].


2. The composition of claim 1 wherein SV≦[(0.703×CRI)-0.80)].
 3. Thecomposition of claim 1 wherein SV≦[(0.703×CRI)-1.55)].
 4. Thecomposition of claim 1 wherein the composition comprises apolyorganosiloxane microemulsion comprising:(i) a polyorganosiloxanedispersed as particles in the microemulsion, the polyorganoiloxanehaving an average particle size of less than about 150 nanometers, and(ii) a surfactant system for dispersing the organopolysiloxane in themicroemulsion; wherein the amount of microemulsion is such that thepersonal care composition comprises from about 0.01% to about 10% of thepolyorganosiloxane.
 5. The composition of claim 1 wherein the firstsolvent is water.
 6. The composition of claim 5 wherein the compositioncomprises said second solvent, wherein the second solvent is selectedfrom the group consisting of C₁ -C₃ monohydric alcohols and mixturesthereof.
 7. The composition of claim 6 wherein the composition comprisesfrom about 0.5% to about 40%, by weight of the composition, ofmonohydric alcohol.
 8. The composition of claim 7 wherein thecomposition comprises less than about 16%, by weight of the composition,of monohydric alcohol.
 9. The composition of claim 6 wherein thecomposition comprises less than about 6%, by weight of the composition,of monohydric alcohol.
 10. The composition of claim 5 wherein thecomposition comprises from about 10% to about 99%, by weight of thecomposition, of water.
 11. The composition of claim 1 wherein the hairstyling polymer is selected from the group consisting of (i) linear,silicone block copolymers; (ii) silicone graft copolymers comprising alinear, non-silicone polymeric backbone having a silicone macromonomerside chain; (iii) silicone graft copolymers comprising a linear,silicone polymeric backbone having a non-silicone macromonomer sidechain; and (iv) mixtures thereof.
 12. The composition of claim 11wherein the hair styling polymer is a silicone graft copolymercomprising a linear, non-silicone polymeric backbone having a siliconemacromonomer side chain.
 13. The composition of claim 12 wherein thesilicone polymer is a silicone graft copolymer having a weight averagemolecular weight of from about 10,000 to about 1,000,000, and having avinyl polymeric backbone having grafted to it monovalent siloxanepolymeric moieties, the copolymer comprising C monomers and componentsselected from the group consisting of A monomers, B monomers, andmixtures thereof, wherein:A is at least one free radically polymerizablevinyl monomer, the amount by weight of A monomer, when used, being up toabout 98% by weight of the total weight of all monomers in saidcopolymer; B is at least one reinforcing monomer copolymerizable with A,the amount by weight of B monomer, when used, being up to about 98% ofthe total weight of all monomers in said copolymer, said B monomer beingselected from the group consisting of polar monomers and macromers; atleast one of said A or B monomers comprising acrylate groups; and C is apolymeric monomer having a weight average molecular weight of from about1,000 to about 50,000 and the general formula

    X(Y).sub.n Si(R).sub.3-m (Z).sub.m

whereinX is a vinyl group copolymerizable with the A and B monomers, Yis a divalent linking group, R is a hydrogen, lower alkyl, aryl oralkoxy, Z is a monovalent siloxane polymeric moiety having a numberaverage molecular weight of at least about 500, is essentiallyunreactive under copolymerization conditions, and is pendant from saidvinyl polymeric backbone after polymerization, n is 0 or 1, m is aninteger from 1 to 3, wherein C comprises from about 0.01% to about 50%by weight of the copolymer.
 14. The composition or claim 1 wherein thecomposition comprises a silicone-polyoxyalkylene copolymer surfactant.15. A personal care composition suitable for styling hair comprising:a)from about 0.01% to about 6% by weight of the composition, of a hairstyling polymer b) a polyorganosiloxane microemulsion comprising:(i) apolyorganosiloxane dispersed as particles in the microemulsion, thepolyorganoiloxane having an average particle size of less than about 150nanometers, and (ii) a surfactant system for dispersing theorganopolysiloxane in the microemulsion; wherein the amount ofmicroemulsion is such that the personal care composition comprises fromabout 0.01% to about 10% of the polyorganosiloxane; c) a primary solventsystem for the hair styling polymer comprising:i) from about 5% to about99%, by weight of the composition, of water; and ii) from about 0.5% toabout 55%, by weight of the composition, of a second solvent selectedfrom the group consisting of C1-C3 monohydric alcohols and mixturesthereof; and d) from about 0.01% to about 200%, by weight of the hairstyling polymer, of a plasticizer; wherein the composition ischaracterized by having a Stiffness Value (SV) and a Curl RetentionIndex (CRI), wherein

    SV≧[(0.703×CRI)-0.425)].


16. 16. The composition of claim 1 in the form of a gel.
 17. Thecomposition of claim 1 in the form of a mousse.